JP3500474B2 - Optical information recording medium - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical information recording medium (hereinafter also abbreviated as a recording medium) used for a computer memory, a memory for image and sound files, an optical card and the like.

[0002]

2. Description of the Related Art A recording medium having an organic dye thin film as a recording layer is known in which a phthalocyanine compound is used for the organic dye thin film (Japanese Patent Laid-Open No. 183296/1983). 58-37851
No. Phthalocyanine compounds have the advantage of being extremely highly stable to heat and light, but have poor solubility in organic solvents, etc., and conventionally they can only be formed into thin films by the vapor deposition method, resulting in difficulty in productivity and easy association. , High refractive index,
There is a problem that a high reflectance cannot be obtained.

On the other hand, in recent years, semiconductor lasers having an oscillation wavelength (up to 680 nm) shorter than the wavelength range used in conventional optical disks have been put into practical use in order to achieve higher recording density. However, there is no conventional organic dye thin film having a light absorption ability and a light reflection ability in a wavelength range of 700 nm or less, and there is a limitation in high density recording property in terms of material.

Further, in a write-once compact disc type (CD-R) recording medium in which an organic dye thin film, a metal reflection layer and a protective layer are sequentially laminated on a substrate, a high reflectance is required to satisfy the CD standard. Therefore, it was necessary to develop an organic dye material having a high refractive index in the reproduction wavelength range (700 to 830 nm) and high stability.

Recently, in order to prevent the association of the phthalocyanine compound and achieve a high refractive index, it has been attempted to introduce a bulky alkoxy group at the α-position of phthalocyanine, and a halogenated phthalocyanine is used for wavelength matching. A measured CD-R type recording medium has been proposed (JP-A-3-
62878, 3-215466, 4-3481.
No. 68, No. 4-226390, No. 4-15263 to 6
No. 5, No. 5-17477, No. 5-86301, No. 5-
No. 25177, No. 5-25179, No. 5-17700.
Nos. 5-1272, etc.). Although such a phthalocyanine compound certainly brings about an improvement in the refractive index and the like, it is not yet sufficiently satisfied, and further improvement is desired.

Therefore, a first object of the present invention is to record a phthalocyanine compound having a high solubility in an organic solvent and a high productivity and a solvent coatable phthalocyanine compound as a recording material, while utilizing the characteristics of the phthalocyanine compound. To provide the medium. A second object of the present invention is 630 which enables high density recording.
It is an object of the present invention to provide a recording medium applicable to an optical pickup using a semiconductor laser of up to 700 nm. A third object of the present invention is to provide a recording medium which has a high refractive index in the wavelength range of 770 to 830 nm and which can achieve a CD-R medium having a high reflectance and excellent storage stability and reproduction stability. To provide.

[0007]

[Means for Solving the Problems] A phthalocyanine compound is a macrocyclic planar compound and has an extremely high association property. Therefore, when it is made into a thin film, the absorption spectrum becomes broad and the reflectance (refractive index) also becomes low. is doing. Therefore, the present invention introduces a substituent having a sterically bulky structure as a substituent of the ring, prevents association, realizes high absorptivity and high reflectance (refractive index), and is suitable for organic solvents. It also has improved solubility.

That is, according to the present invention, in the optical information recording medium, a recording layer is provided on a substrate directly or via an undercoat layer, and further a protective layer is provided on the recording layer, if necessary. There is provided an optical information recording medium characterized by containing a phthalocyanine compound represented by the following general formula (I) therein.

[Chemical 1] Wherein, M, X ¹ to X ⁴ and k~n represent the following, respectively. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ⁴ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, or silyl group, k, l, m, n: each independently an integer of 0 to 4, but not all 0 at the same time, k , L, m and n are 3 or less, the other substituent on the benzene ring is a hydrogen atom or a halogen atom. ]

According to the present invention, the phthalocyanine compound is represented by the following general formulas (IIa) to (IId).
Among the species, it is characterized by being composed of one kind or a mixture of two or more kinds.
The above-mentioned optical information recording medium is provided.

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5] [In the formula, M and X ^{1 to} X ¹⁶ respectively represent the following. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, silyl group, or atom other than X ^{1 to} X ¹⁶ on benzene ring: Hydrogen atom is a halogen atom. ]

Further, according to the present invention, the phthalocyanine compound is represented by the following general formulas (IIIa) to (IIId):
Among the species, it is characterized by being composed of one kind or a mixture of two or more kinds.
The above-mentioned optical information recording medium is provided.

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9] [In the formula, M and X ^{1 to} X ¹⁶ respectively represent the following. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, silyl group, or atom other than X ^{1 to} X ¹⁶ on benzene ring: Hydrogen atom is a halogen atom. ]

According to the present invention, the phthalocyanine compound is represented by the following general formulas (IVa) to (IVd).
Among the species, it is characterized by being composed of one kind or a mixture of two or more kinds.
The above-mentioned optical information recording medium is provided.

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13] ^{Wherein, M, X 1 ~X 16,} Y and n1~n4 represent the following, respectively. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, silyl group, or atom other than X ^{1 to} X ¹⁶ on benzene ring: Hydrogen atom is a halogen atom. Y: halogen atom, n1 to n4: each independently represent the number of halogen substitutions,
An integer from 1 to 4. ]

Further, according to the present invention, a write-once compact disc type recording medium is provided which is provided with a metal reflection layer between the recording layer and the protective layer and records a CD format signal. An optical information recording medium is provided.

The phthalocyanine compound used in the present invention has excellent association inhibiting ability (carbon atom) because the silyl substituents represented by X ^{1 to} X ¹⁶ are introduced into the benzene ring of the phthalocyanine skeleton as bulky substituents. Since the silicon atom is larger than that of the α-alkoxy phthalocyanine, the phthalocyanine used in the present invention is superior in association inhibiting ability to the α-alkoxy phthalocyanine) and is also excellent in light resistance. Therefore, the CD-R recording medium using the present phthalocyanine has a high reflectance and excellent storage stability and reproduction stability because it has a high refractive index at wavelengths of 770 to 830 nm and high stability. In addition, wavelengths 630 to 630
Has high absorption and light reflectivity at 720 nm, and 630 to 7
Since it can be applied to a pickup using a 20 nm semiconductor laser, the density can be increased by 1.6 to 1.7 times that of the current recording medium compatible with 770 to 830 nm. Furthermore, due to the effect of the silyl substituent, when the phthalocyanine of the present invention is used as a CD-R medium, the carbon-silicon bond is weaker than the carbon-carbon bond, and the carbon-silicon bond is cut during recording, and The signal characteristics are good.

The present invention will be described in detail below. 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, in which a recording layer 2 is provided on a substrate 1 with an undercoat layer 3 interposed if necessary, and further protected if necessary. Layer 4 is provided.

FIG. 2 is a diagram showing an example of another type of layer structure applicable to the recording medium of the present invention. The recording layer 2 having the structure shown in FIG.
The metal reflection layer 5 is provided on the top surface.

The recording medium of the present invention may have an air sandwich structure in which the recording layer (organic thin film layer) having the structure shown in FIGS. 1 and 2 is placed inside and sealed with another substrate through a space, Alternatively, a laminated structure in which the protective layer is adhered may be used.

Next, the required characteristics of the constituent layers and the constituent materials thereof 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 light used, but it is not necessary to be transparent when recording / reproducing is performed from the recording layer side. As the substrate material, for example, polyester,
Acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, plastic such as polyimide, glass, ceramic or metal can be used. In addition, a guide groove or a guide pit for tracking and a preformat such as an address signal may be formed on the surface of the substrate.

2) Recording layer The recording layer is capable of recording some information by causing some kind of optical change by irradiation of laser light, and the phthalocyanine compound of the general formula (I) is contained in this recording layer. Must be included. In forming the recording layer, the compounds of the present invention may be used alone or in combination of two or more. Further, the compound of the present invention is another dye, for example, polymethine dye, naphthalocyanine type, squarylium type, croconium type, pyrylium type, naphthoquinone type, anthraquinone (indanthrene) type, xanthene type, triphenylmethane type, azulene type, You may use it combining with a tetrahydrocholine type | system | group, a phenanthrene type | system | group, a triphenothiazine type | system | group dye, or a metal complex compound. In this case, the above dyes may be used alone or in combination of two or more.

Further, the compound of the present invention is a metal, a metal compound such as In, Al, Te, Bi, Al, Be, Te.
O ₂ , SnO, As, Cd and the like can also be used in the form of dispersion mixing or lamination. Further, various materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, or silane coupling agents may be dispersed and mixed in the compound of the present invention. Or for the purpose of improving properties, stabilizers (for example, transition metal complexes), dispersants, flame retardants,
It can be used together with a lubricant, an antistatic agent, a surfactant, a plasticizer and the like.

The recording layer is formed by vapor deposition, sputtering, C
It can be done by conventional means such as VD or solvent coating. When the coating method is used, the above compounds and the like are dissolved in an organic solvent, and a conventional coating method such as spraying, roller coating, dipping or spinner coating is used. As the organic solvent, generally, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexane,
Amides such as N, N-dimethylacetamide and N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, 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, aromatics such as benzene, xylene, monochlorobenzene and dichlorobenzene, or cellsolves such as methylcellosolve and ethylcellosolve Can be used. The thickness of the recording layer is 100Å to 10 μm, preferably 2 in the case of the medium structure shown in FIG.
00 Å to 1000 Å is suitable, and 300 Å to 5 μm, preferably 500 Å to the medium configuration shown in FIG.
2000Å is suitable.

3) Undercoat layer The undercoat layer has (a) improved adhesion, (b) barrier against water or gas, (c) improved storage stability of the recording layer, and (d) improved reflectance. , (E) protection of the substrate from solvent, (f) formation of guide grooves, guide pits, preformats, etc. For the purpose of (a), it is possible to use various polymers such as ionomer resins, polyamides, vinyl resins, natural resins, natural polymers, silicones, liquid rubbers, and various silane coupling agents. For the purposes of (b) and (c), an inorganic compound such as SiO 2 in addition to the above-mentioned polymer material
₂ , MgF ₂ , SiO, TiO ₂ , ZnO, TiN, Si
N, Zn, Cu, Ni, Cr, Ge, Se, Au,
A metal such as Ag or Al or a semi-metal can be used. For the purpose of (b), a metal such as A
l, Ag, or the like, or an organic thin film having a metallic luster, such as a methine dye or a xanthene dye, can be used.
For the purposes of (e) and (f), 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 0.1.
05-10 μm is suitable.

4) Metal Reflective Layer For the metal reflective layer, a metal, a semi-metal, or the like, which has a high reflectance and is hardly corroded, can be used. As a specific material,
Au, Ag, Cu, Al, Cr, Ni, etc. are mentioned,
Au and Al are preferable. These metals and semimetals may be used alone or as an alloy of two or more kinds.
Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 3000 Å, preferably 100.
It is ~ 1000Å.

5) Protective layer, substrate surface hard coat layer The protective layer or substrate surface hard coat layer protects the recording layer from (a) scratches, dust, dirt, etc. (b) Improves storage stability of the recording layer , (C) used for the purpose of improving the reflectance. For these purposes, the materials shown in the undercoat layer can be used. In addition, as an inorganic material, S
It is also possible to use iO, SiO _2, etc., and as an organic material, acrylic resin, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, natural rubber, styrene-butadiene. Resins, chloroprene rubber, waxes, alkyd resins, drying oils, heat-softening and heat-melting resins such as rosin can also be used. Among the above materials, the most preferable one for the protective layer or the substrate surface hard coat layer is an ultraviolet curable resin having excellent productivity. The thickness of the protective layer or the substrate surface hard coat layer is 0.01 to 30 μm.
m, preferably 0.05 to 10 μm. In the present invention, the undercoat layer and the protective layer may contain a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, etc., as in the case of the recording layer. .

In the present invention, the phthalocyanine compound represented by the general formula (I) is contained in the recording layer.
In the general formula (I), the metal atom represented by M is Al, Si, Ca, Cd, Ti, V, Mn, Fe,
Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, P
There are d, In, Sn, Pt, Pb and the like. Specific examples of the compound represented by the general formula (I) are shown in Table 1
Examples include those shown in [Table 1- (1) and Table 1- (2)].

[0025]

[Table 1- (1)]

[0026]

[Table 1- (2)]

The compound represented by the general formula (I) can be obtained by reacting the corresponding phthalocyanine compound or diiminoisoindoline compound with the above metal or its derivative in an organic solvent. Further, in the general formula (I), when M is two hydrogen atoms,
It is obtained by reacting the corresponding phthalonitrile compound or diiminoisoindoline compound with lithium or sodium.

The compound represented by the general formula (IIa) used in the present invention is represented by the general formula (IIa) from the viewpoints of the matching of the absorption wavelength of phthalocyanine and the yield when used in an optical information recording medium. To (IId), one consisting of one or a mixture of two or more kinds, or a mixture of one or two or more kinds out of the four kinds represented by the general formulas (IIIa) to (IIId). Those consisting of are preferred. One kind or a mixture of two or more kinds represented by the general formulas (IIa) to (IId) and (IIIa) to (IIId) is a phthalonitrile compound or a diiminoisoindoline compound corresponding to 1 to 4 kinds of the metal. Alternatively, it can be obtained by reacting the derivative with an organic solvent.

Further, the compound represented by the general formula (I) used in the present invention is represented by the above general formulas (IVa) to (IVd) from the viewpoint that the absorption maximum wavelength can be made longer. Those composed of one kind or a mixture of two or more kinds are preferable. One or two of these general formulas (IVa) to (IVd)
Mixtures of one or more are (IIa) to (IId) and (IIIa) to (III
It can be obtained by halogenating one or more of d). For the halogenation reaction in this case, the examples described in JP-A-3-62878 can be used as they are.

General formulas (IIa) to (IId), (IIIa) to (IIId)
Specific examples of the compounds represented by (IVa) to (IVd) include those shown in Table 2 [Table 2- (1) and (Table 2- (2)]. Although the compounds shown have isomers as described above, they are not listed in Table 2.

[0031]

[Table 2- (1)]

[0032]

[Table 2- (2)]

[0033]

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A polymethylmethacrylate plate having a thickness of 1.2 mm was photopolymerized to have a depth of 1000 Å and a half value width of 0.4 μ.
m and the track pitch of 1.4 μm, the compound No. The 1,2-dichloroethane solution of No. 1 was applied to a spinner, and a recording layer having a thickness of 800 Å was provided to obtain a write-once recording medium.

Examples 2 to 6 In Example 1, the compound Nos. Instead of 1.
Compound No. 6, No. 10, No. 1
1, No. 12, No. Recording media of Examples 2 to 6 were obtained in the same manner as in Example 1 except that No. 18 was used.

Comparative Example 1 In Example 1, the compound No. A recording medium of Comparative Example was obtained in the same manner as in Example 1 except that a phthalocyanine compound represented by the following formula (V) was used instead of 1.

[Chemical 14] (However, in the formula, t-Bu is 2 to 2 '''' and 3 to
It is a mixture of 3 '''positions. )

Using the recording media of Examples 1 to 6 and Comparative Example 1 described above, recording was performed through the substrate under the following recording conditions, and then the recording position was reproduced with continuous laser light, and C was recorded under the following conditions. / N was measured. The reflectance was also measured. The results are shown in Table 2. Recording conditions: linear velocity 2.1 m / sec recording frequency 1.25 MHz laser oscillation wavelength 680 nm pickup lens N.P. A. 0.5 Playback condition: Scanning filter 30KHz Bandwidth playback power 0.25-0.3mW

[0038]

[Table 3]

Example 7 On a 1.2 mm thick injection-molded polycarbonate substrate having a guide groove with a depth of 1000 Å, a half width of 0.45 μm and a track pitch of 1.6 μm, the compound No. 1,2,2,2-trifluoroethanol / 1,2-dichloroethane / 2-methoxyethanol (= 7 / 1.5 /
1.5 (weight ratio)) mixed solution is applied by spinner, thickness 1
An 800 Å recording layer is provided, and 1100 Å Au is vacuum-deposited on the recording layer to form a reflective layer, and an acrylate photopolymer is spinner coated on the reflective layer to form a protective layer having a thickness of about 3 μm. It was used as a recording medium.

Examples 8 to 12 In Example 7, the compound Nos. 1 instead of compound No. 1 in the table. 2, No. 5, No. 6, N
o. 8, No. Recording media of Examples 8 to 12 were obtained in the same manner as in Example 7 except that No. 16 was used.

Comparative Example 2 In Example 7, the compound No. Example 7 except that the phthalocyanine of Comparative Example 1 was used instead of 1.
A recording medium of Comparative Example was obtained in the same manner as in.

Comparative Example 3 In Example 7, the compound No. Example 7 except that the compound of the following general formula (VI) was used in place of 1.
A recording medium of Comparative Example was obtained in the same manner as in.

[Chemical 15]

Comparative Example 4 In Example 7, the compound No. Instead of 1.
A recording medium of a comparative example was obtained in the same manner as in Example 7 except that 10% by weight of the nickel complex compound of the following formula (VII) was added to the compound of the above formula (VI).

[Chemical 16]

Using the recording media of Examples 8 to 12 and Comparative Examples 2 to 4, wavelength 790 nm, linear velocity 1.4 m / sec.
The EFM signal was recorded under the recording conditions of _{No. 1,} and the reflectance and the number of C ₁ errors before recording and after irradiation with tungsten light were measured. The results are shown in Table 4.

[0045]

[Table 4]

Production Example 1 10 g of phthalonitrile represented by the following formula (VIII) was added to 3
The mixture was dissolved in 2 g of hexanol by heating, 4 g of diazabicyclononene was added, 1.8 g of nickel chloride was further added, and the mixture was stirred at 120 to 130 ° C. for 24 hours in an Ar atmosphere. The reaction product was cooled to room temperature, the insoluble matter was filtered off, the hexanol in the filtrate was dried as much as possible, and the mixture was subjected to the following formulas (1A) (1B) (1
(1A) / (1B) / (1 shown by C) and (1D)
C) / (1D) = 30/48/22/0 mixture 5.6
g (yield 52.6%) was obtained. The λmax of this mixture in chloroform was 700 nm.

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

Production Example 2 10 g of phthalonitrile represented by the following formula (IX)
g of butanol under heating, then 4.1 g of diazabicycloundecene was added, and further 1.7 g of copper chloride was added,
The mixture was heated under reflux for 36 hours in an Ar atmosphere. The reaction product was cooled to room temperature, the insoluble matter was filtered off, the butanol in the filtrate was distilled off, and the solution was converted to the following formula (2) with a toluene / silica gel column.
(A) (2B) (2C) and (2D) shown by (2D)
/ (2B) / (2C) / (2D) = 38/42/15 /
6.8 g of a mixture of 5 (63.6% yield) was obtained. In addition,
The λmax of this mixture in chloroform is 682 nm.
Met.

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

Production Example 3 10 g of diiminoisoindoline represented by the following formula (X)
Was dissolved in 30 g of n-amyl alcohol by heating, 2 g of palladium chloride was added, and the mixture was heated under reflux in an Ar atmosphere to give 28
Stir for hours. The reaction product was cooled to room temperature, the insoluble matter was collected by filtration, the amyl alcohol in the filtrate was dried, and the mixture was subjected to the following formulas (3A) (3B) (3) with a toluene / silica gel column.
(3A) / (3B) / (3 shown by C) and (3D)
C) / (3D) = 40/40/20/0 mixture 6.2
g (yield 59.7%) was obtained. The λmax in chloroform of this mixture was 693 nm.

[0053]

[Chemical 27]

[0054]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

Production Example 4 25 g of 10 g of phthalonitrile represented by the following formula (XI)
g of n-amyl alcohol was dissolved by heating, 4.5 g of diazabicycloundecene was added, and then 2.3 g of palladium chloride was added thereto.
Stir for hours, cool the reaction mixture to room temperature, filter off insolubles, dry the amyl alcohol in the filtrate, and remove toluene /
In a silica gel column, the following formulas (4A) (4B) (4
(4A) / (4B) / (4 shown by C) and (4D)
C) / (4D) = 10/80/10/0 mixture 4.
8 g (yield 43.3%) was obtained. The λmax in chloroform of this mixture was 699 nm.

[0056]

[Chemical 32]

[0057]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

Production Example 5 10 g of phthalonitrile represented by the following formula (XII) was added to 40
g in n-amyl alcohol by heating, diazabicycloundecene 4 g was added, then palladium chloride 2 g was added, and the mixture was stirred at 115 to 130 ° C. for 27 hours under Ar atmosphere, and the reaction product was cooled to room temperature, Insoluble matter is filtered off,
The amyl alcohol in the filtrate was dried, and toluene / chloroform = 1/1 (volume ratio) / silica gel column was used to represent (5A) / (5B) represented by the following formulas (5A) (5B) (5C) and (5D). / (5C) / (5D) = 20/80
5.8 g (yield 52.6%) of a mixture of / 0/0 was obtained.
The λmax of this mixture in chloroform was 69.
It was 1 nm.

[0059]

[Chemical 37]

[0060]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

[Chemical 41]

Production Example 6 The phthalocyanine mixture obtained in Production Example 3 was dissolved by heating in a mixed solvent of dichloromethane and water, and bromine was added to the mixture to give the following formulas (6A) (6B) (6C) and (6
(6A) / (6B) / (6C) / (6 shown by D)
D) = 40/40/20/0 mixture was obtained. The λmax in chloroform was 707 nm, which was a long wavelength.
The phthalocyanine mixture obtained in Examples 7, 8, 10 and 11 can also be halogenated.

[0062]

[Chemical 42]

[Chemical 43]

[Chemical 44]

[Chemical formula 45]

Example 13 On a 1.2-mm-thick polymethylmethacrylate plate, a photopolymer was used, and the depth was 1000Å and the half-value width was 0.4 μm.
m, track pitch of 1.4 μm, a 1,2-dichloroethane solution of the mixture of the formulas (6A) to (6D) was spinner coated on a substrate having a guide groove formed thereon, and a recording layer having a thickness of 1000 Å was provided for additional writing. Type recording medium.

Examples 14 to 17 In Example 13, instead of the mixture of the formulas (6A) to (6D), the compound No. of the above Table 2 was used. 25, N
o. 28, No. 29, No. Recording media of Examples 14 to 17 were obtained in the same manner as in Example 13 except that 36 was used.

Comparative Example 5 Comparative Example 5 was repeated in the same manner as in Example 13 except that a phthalocyanine compound represented by the following formula (XIII) was used in place of the mixture of the formulas (6A) to (6D). An example recording medium was obtained.

[Chemical formula 46]

Using the recording media of Examples 13 to 17 and Comparative Example 5 described above, recording was performed through the substrate under the following recording conditions,
Then, the recording position was reproduced with a continuous laser beam, and the C / N was measured under the following conditions. The reflectance was also measured. The results are shown in Table 5. Recording conditions: linear velocity 2.1 m / sec recording frequency 1.25 MHz laser oscillation wavelength 680 nm pickup lens N.P. A. 0.5 Playback condition: Scanning filter 30KHz Bandwidth playback power 0.25-0.3mW

[0067]

[Table 5]

Example 18 Thickness 1.2 mm, groove depth 1000 Å, half width 0.45 μ
m and a 1.2 mm thick injection-molded polycarbonate substrate having guide grooves with a track pitch of 1.6 μm, the mixture of the above formulas (6A) to (6D) was mixed with ethyl cellosolve / T.
Dissolve it in a mixed solution of HF, apply it with a spinner, provide a recording layer with a thickness of 1800 Å, and further add 110 Au on it.
A reflective layer was vacuum-deposited to a thickness of 0Å, and an acrylate-based photopolymer was applied onto the reflective layer by spinner to form a protective layer having a thickness of about 6 μm to obtain a CD-R type recording medium.

Examples 19 to 22 In Example 18, instead of the mixture of formulas (6A) to (6D), the compound No. 25, no.
26, No. 36, No. Recording media of Examples 19 to 22 were obtained in the same manner as in Example 18 except that 38 was used.

Comparative Example 6 In Example 18, a mixture of brominated alkoxyphthalocyanine isomers 2/8 represented by the following formulas (XIVa) and (XIVb) was used instead of the mixture of formulas (6A) to (6D). A recording medium of a comparative example was obtained in the same manner as in Example 18 except for the above.

[Chemical 47]

[Chemical 48]

Comparative Example 7 In Example 18, a mixture of brominated alkoxyphthalocyanine isomers 2/8 represented by the following formulas (XIVc) and (XIVd) was used instead of the mixture of formulas (6A) to (6D). A recording medium of a comparative example was obtained in the same manner except for the above.

[Chemical 49]

[Chemical 50]

Using the recording media of Examples 18 to 22 and Comparative Examples 6 to 7, the laser oscillation wavelength was 790 nm and the linear velocity was 1.4.
The EFM signal was recorded under the recording condition of m / sec, the C ₁ error at the optimum recording power Po and the optimum recording power × 0.82 was measured, and further 75,000 Lux light at Po and the C after 700 hours were measured. _The number of errors was measured. The results are shown in Table 6.

[0073]

[Table 6]

[0074]

【The invention's effect】

1) High light absorption and light reflectivity at wavelengths of 630 to 700 nm, so that high density recording is possible at 630 to 700 n
It is a recording medium that can be applied to a pickup using a m laser, and a recording density of 1.6 to 1.7 times higher than that of the current recording medium compatible with 780 to 810 nm can be achieved. 2) Since it has a high refractive index at a wavelength of 770 to 830 nm and a high stability, it is possible to provide a recording medium for CD-R which has a high reflectance and is excellent in storage stability and reproduction stability.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a layer structure applicable to a recording medium of the present invention.

FIG. 2 is a diagram showing an example of another type of layer structure applicable to the recording medium of the present invention.

[Explanation of symbols]

1 substrate 2 Recording layer (organic dye layer) 3 subbing layer 4 protective layer 5 Metal reflective layer

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-64-54069 (JP, A) JP-A-3-13384 (JP, A) JP-A-1-176585 (JP, A) JP-A-3- 71888 (JP, A) JP-A-7-89240 (JP, A) JP-A-62-90291 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B41M 5/26

Claims (5)

(57) [Claims] 1. An optical information recording medium in which a recording layer is provided on a substrate directly or via an undercoating layer, and a protective layer is further provided on the recording layer, if necessary, in the recording layer. An optical information recording medium containing the phthalocyanine compound represented by I). [Chemical 1] Wherein, M, X ¹ to X ⁴ and k~n represent the following, respectively. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ⁴ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted An aliphatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a silyl group, k, l, m, and n: each independently an integer of 0 to 4, but not all 0 at the same time; , L, m and n are 3 or less, the other substituent on the benzene ring is a hydrogen atom or a halogen atom. ] Wherein among the four that the phthalocyanine compound represented by the following general formula (IIa) ~ (IId), according to claim 1, characterized in that it consists of one or a mixture of two or more <br /> Optical information recording medium. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [In the formula, M and X ^{1 to} X ¹⁶ respectively represent the following. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, or silyl group, atom other than X ^{1 to} X ¹⁶ on benzene ring: Hydrogen atom is a halogen atom. ] 3. The phthalocyanine compound is one or two of four types represented by the following general formulas (IIIa) to (IIId).
2. A mixture of at least one species.
Of the optical information recording medium. [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [In the formula, M and X ^{1 to} X ¹⁶ respectively represent the following. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, silyl group, or atom other than X ^{1 to} X ¹⁶ on benzene ring: Hydrogen atom is a halogen atom. ] 4. Of the four said phthalocyanine compound is represented by the following general formula (IVa) ~ (IVd), according to claim 1, characterized in that it consists of one or a mixture of two or more <br /> Optical information recording medium. [Chemical 10] [Chemical 11] [Chemical 12] [Chemical 13] ^{Wherein, M, X 1 ~X 16,} Y and n1~n4 represent the following, respectively. M: two hydrogen atoms, a metal atom which may have a halogen atom or an oxygen atom, or-(OR ⁵ ) p or-(O
SiR ⁶ R ⁷ R ⁸ ) q may have a metal atom, R ^{5 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group Or a substituted or unsubstituted aromatic heterocyclic group, p, q: an integer of 0 to 2, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : independently substituted. Or an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aliphatic hydrocarbon group having an ether bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ² To R ⁴ : each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR ⁹ group, R ⁹ : hydrogen atom, substituted or unsubstituted Aliphatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, or silyl group, atom other than X ^{1 to} X ¹⁶ on benzene ring: Hydrogen atom is a halogen atom. Y: halogen atom, n1 to n4: each independently represent the number of halogen substitutions,
An integer from 1 to 4. ] 5. A write-once compact disc type recording medium for recording a CD format signal, comprising a metal reflection layer provided between the recording layer and the protective layer. The optical information recording medium according to any one of items.