JP3493479B2 - Optical 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 recording medium (hereinafter also referred to as a recording medium) used for a computer memory, a memory for image and audio 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).
No. 58-37851). 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. However, there is a problem that a high refractive index and 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.).

[0006]

However, although these phthalocyanine compounds certainly bring about an improvement in the refractive index and the like, they are not yet sufficiently satisfied, and further improvement is desired.

Therefore, the first object of the present invention is to record a phthalocyanine compound having a high solubility in an organic solvent, 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 to provide a recording medium applicable to an optical pickup using a 630 to 720 nm semiconductor laser capable of high density recording. Furthermore, a third object of the present invention is to achieve a high reflectance CD-R medium which has a high refractive index in the wavelength range of 770 to 830 nm and is excellent in storage stability and reproduction stability. To provide the medium.

[0008]

[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 to the phthalocyanine ring to prevent association.
High solubility and high reflectance (refractive index) are realized, and the solubility in organic solvents is improved. Further, when a substituent other than the above substituents is a fluorine-substituted alkyl group, further solubility is improved. This improves the signal quality.

That is, according to the present invention, firstly, in an optical recording medium in which a recording layer is provided on a substrate directly or via an undercoat layer, and further, a protective layer is provided thereon if necessary. There is provided an optical recording medium characterized in that the recording layer contains at least one kind of a phthalocyanine compound represented by the following general formula (I).

[Chemical 1] [In the formula, M, X ^{1 to} X ⁴ , R ^{1 to} R ⁴ , Y ^{1 to} Y ⁴ , k to n, and o to r each represent the following. M: 2 hydrogen atoms, a halogen atom or an oxygen atom a bivalent which may contain, trivalent or tetravalent metal atom, or - (OR ⁵⁾ s ^{group, - (OSiR 6 R 7 R} 8) t Group,-(OCO
R ⁹ ) u group or a metal atom which may have a — (OPOR ¹⁰ R ¹¹ ) v group, R ^{5 to} R ¹¹ : each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or Substituted or unsubstituted monovalent aromatic hydrocarbon group, s, t, u, v: an integer of 0 to 2, X ^{1 to} X ⁴ : each independently an oxygen atom or a sulfur atom, R ^{1 to} R ⁴ : each: Independently linear, branched or alicyclic alkyl group having 1 to 20 C's, optionally substituted, silyl group or optionally substituted aryl group, Y ^{1 to} Y ⁴ : independently C 1's ~ 14 fluorine-substituted alkyl group or fluorine-substituted oxaalkyl group, k, l, m, n: represents the number of substitution, an integer of 0-2, provided that all of k, l, m, n are 0 at the same time. O, p, q, r: represents the number of substitutions, an integer of 0 to 1, provided that o, p q, is not equal to 0 at the same time all of the r, should be noted that when the k + l + m + n + o + p + q + r <16,
The other substituent on the benzene ring is a hydrogen atom or a halogen atom. )

Secondly, in the optical recording medium described in the first item, a write-once compact disc type recording medium which is provided with a metal reflection layer between a recording layer and a protective layer and records a CD format signal. An optical recording medium is provided.

Thirdly, in the optical recording medium described in the first or second, in the recording layer, k = 1 = m = n = 1 in the general formula (I), and the substitution position is 1 or X ¹ R ^{1 to} X ^{4 of the} benzene ring, which is the position represented by ⁴
Substituents other than those substituted by R ⁴ or Y ^{1 to} Y ⁴ contain a compound which is a hydrogen atom or a halogen atom, and the absorption maximum wavelength (λmax) of the recording layer is 680 to 7
Fourthly, an optical recording medium having a thickness of 50 nm is provided. Fourthly, in the optical recording medium described in the first, the recording layer has k = 1 / m = n = 1 in the general formula (I), a position where the substitution position is displayed as 2 or 3, and substituents other than substituted with X ¹ R ¹ ~X ⁴ R ⁴ or Y ¹ to Y ⁴ of the benzene ring is a hydrogen atom or a halogen atom An optical recording medium containing the compound is provided.

Fifth, in the optical recording medium described in the above first, third or fourth, the recording layer has wavelengths of 630 to 7.
There is provided an optical recording medium which is recorded and reproduced by a laser beam of 20 nm, and sixthly, in the optical recording medium described in the above second or third, the recording layer has a wavelength of 770 to 830 nm. An optical recording medium is provided that is recorded and reproduced by the optical recording medium.

The present invention will be described in detail below. The optical recording medium of the present invention is characterized in that the recording layer contains at least one of the phthalocyanine compounds represented by the general formula (I). The phthalocyanine compound used in the present invention is excellent in association inhibition ability, high absorption ability and high reflection ability because the substituent represented by X ¹ R ¹ or the like is introduced into the benzene ring of the phthalocyanine skeleton as a bulky substituent. The solubility (refractive index) is improved, the solubility in an organic solvent is improved, and the fluorine-substituted alkyl group represented by Y ¹ or the like is introduced as another substituent. And improvement in signal quality can be achieved by the change in adhesion to the substrate due to the influence of fluorine. That is, this phthalocyanine compound has a wavelength of 630 to 720.
having high absorptivity and light reflectivity in nm, 630 to 720n
The write-once type optical recording medium using the compound is applicable to a pickup using a semiconductor laser of m.
Compared with a recording medium compatible with 70 to 830 nm, 1.6 to 1.
8 times higher density is possible.

Further, since the phthalocyanine compound represented by the general formula (I) has a high refractive index at a wavelength of 770 to 830 nm and a high stability, a recording layer, a metal reflection layer and a protective layer are sequentially formed on the substrate. When this phthalocyanine compound is used in a laminated CD-R recording medium, it has high reflectance and excellent storage stability and reproduction stability.

Further, in the phthalocyanine compound represented by the general formula (I), the substitution positions 1 and 4 are called α-positions. The α-position has an electron-donating substitution such as an alkoxy, aryloxy, alkylthio or arylthio group. When the group is introduced, the maximum absorption wavelength λmax becomes longer than that of the unsubstituted one, and a write-once type optical recording medium in which λmax matches the recording wavelength is obtained, and a high refractive index at 770 to 830 nm can be measured. A CD-R recording medium is obtained. Also,
When a substituent is introduced at the α-position, the substituent protrudes above and below the phthalocyanine plane, prevents the molecules from associating with each other, and contributes to a higher refractive index, which is particularly suitable for a CD-R recording medium.

In the phthalocyanine compound represented by the general formula (I), the substitution positions 2 and 3 are called β-positions. Even if the electron-donating substituent is introduced at the β-positions, the α-positions are about the same. λmax does not have a long wavelength. Of course, there is a solubilizing effect. Therefore, from the viewpoint of high density, β
The position substitution product is more advantageous.

Next, the structure 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 subbing layer 3 is provided on a substrate 1 if necessary.
The recording layer 2 is provided, and the protective layer 4 is further provided if necessary. Further, a hard coat layer can be provided under the substrate 1 as needed. FIG. 2 is a diagram showing an example of another type of layer structure applicable to the recording medium of the present invention, in which the metal reflection layer 6 is provided on the recording layer 2 having the structure of FIG. In addition,
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 FIG. 1 and FIG. You may make it the laminated structure adhere | attached via.

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 represented by 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. In addition, the compounds of the invention are other dyes,
For example, polymethine dyes, naphthalocyanine dyes, squarylium dyes, croconium dyes, pyrylium dyes, naphthoquinone dyes, anthraquinone (indanthrene) dyes, xanthene dyes, triphenylmethane dyes, azulene dyes, tetrahydrocholine dyes, phenanthrene dyes, triphenothiazine dyes. Alternatively, it may be used in combination with a metal complex compound or the like. 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 cyclohexanone,
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 cellosolves such as methoxyethanol and ethoxyethanol, hexane, Hydrocarbons such as pentane, cyclohexane and methylcyclohexane can be used. A suitable film thickness of the recording layer is 100Å-10 μm, preferably 200Å-2000Å.

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 scratches, dust, dirt, etc. (a) 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. Further, SiO, SiO ₂ or the like can be used as the inorganic material, and acrylic resin, polycarbonate, epoxy resin,
Polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, natural rubber, styrene-butadiene resin, chloroprene rubber,
A heat-softening or heat-melting resin such as wax, alkyd resin, drying oil or 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, the protective layer and the substrate surface hard coat layer are the same as in the case of the recording layer, such as a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant and a plasticizer. Can be included.

In the present invention, as described above, the recording layer contains the phthalocyanine compound represented by the following general formula (I).

[Chemical 1] [In the formula, M, X ^{1 to} X ⁴ , R ^{1 to} R ⁴ , Y ^{1 to} Y ⁴ , k to n, and o to r each represent the following. M: 2 hydrogen atoms, a halogen atom or an oxygen atom a bivalent which may contain, trivalent or tetravalent metal atom, or - (OR ⁵⁾ s ^{group, - (OSiR 6 R 7 R} 8) t Group,-(OCO
R ⁹ ) u group or a metal atom which may have a — (OPOR ¹⁰ R ¹¹ ) v group, R ^{5 to} R ¹¹ : each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or Substituted or unsubstituted monovalent aromatic hydrocarbon group, s, t, u, v: an integer of 0 to 2, X ^{1 to} X ⁴ : each independently an oxygen atom or a sulfur atom, R ^{1 to} R ⁴ : each: Independently linear, branched or alicyclic alkyl group having 1 to 20 C's, optionally substituted, silyl group or optionally substituted aryl group, Y ^{1 to} Y ⁴ : independently C 1's ~ 14 fluorine-substituted alkyl group or fluorine-substituted oxaalkyl group, k, l, m, n: represents the number of substitution, an integer of 0-2, provided that all of k, l, m, n are 0 at the same time. O, p, q, r: represents the number of substitutions, an integer of 0 to 1, provided that o, p q, is not equal to 0 at the same time all of the r, should be noted that when the k + l + m + n + o + p + q + r <16,
The other substituent on the benzene ring is a hydrogen atom or a halogen atom. )

Specific examples of M in the general formula (I) are hydrogen atom; Ca, Mg, Zu, Cu, Ni, Pd,
Divalent metals such as Fe, Pb, Co, Pt, Cd, Ru; halides, hydroxylated compounds, alkoxylated compounds, trialkylsiloxy groups, etc. of trivalent metals such as Al, In, Fe, Ga, Tl, Mn; And Si, Ti, S
n, Cr, Ga, Sn, Mn, Zr, V and other tetravalent metal halides, alkoxy compounds, hydroxyl compounds,
Examples thereof include trialkyl siloxy compounds and oxides.
In the definition of R ^{5 to} R ⁸ , the monovalent aliphatic hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group,
alkyl groups such as t-butyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 2- Examples thereof include alkenyl groups such as pentenyl group. Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a benzyl group. Examples of the substituents include halogen atoms such as fluorine, chlorine and bromine, carbon trifluoride groups, cyano groups and ester groups.

In the general formula (I), R ¹ to
R ^4's each independently represent an optionally substituted linear, branched or alicyclic alkyl group having 1 to 20 C's, a silyl group or an optionally substituted aryl group. Specific examples of the alkyl group The following may be mentioned. Methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-pentyl group, neopentyl group, isoamyl group, 2-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group Group, 4-methylpentyl group, 2-ethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, 3- Ethyl pentyl group, n-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, n-nonyl group, n- Primary alkyl groups such as decyl group and n-dodecyl group; isopropyl group, sec-butyl group, 1-ethylpropyl group, 1-methylbutyl group, , 2-dimethylpropyl group, 1-methylheptyl group, 1-ethylbutyl group, 1,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1-ethyl -2
-Methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-propylbutyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-2-methylbutyl group , 1-propyl-2-methylpropyl group, 1-methylheptyl group, 1
-Ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group, 1-isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group, 1
-Secondary alkyl groups such as methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group; tert-butyl group, tert-
Tertiary alkyl groups such as hexyl group, tert-amyl group, tert-octyl group; cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-
Cycloalkyl groups such as tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group and adamantane group.

Further, these primary and secondary alkyl groups may be substituted with a hydroxyl group or a halogen atom, or may be substituted with the above alkyl group via an atom such as oxygen, sulfur or nitrogen. Good. Examples of the alkyl group substituted through oxygen include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a butoxyethyl group, an ethoxyethoxyethyl group, a phenoxyethyl group, a methoxypropyl group and an ethoxypropyl group. As the alkyl group substituted through sulfur, a methylthioethyl group, an ethylthioethyl group, an ethylthiopropyl group, a phenylthioethyl group, and the like, and the alkyl substituted through a nitrogen atom is a dimethylaminoethyl group. , Diethylaminoethyl group, diethylaminopropyl group and the like. Moreover, as an alicyclic alkyl group, an adamantyl group, 1-chloro-
Via an adaman residue such as 2-adamantyl group, 2-chloro-1-adamantyl group, 1-bromo-2-adamantyl group or the like, which may be substituted or methylene group described in Japanese Patent Application No. 7-47806. Examples thereof include a cyclic hydrocarbon group selected from an optionally substituted bornane residue, norbornane residue and norbonnene residue.

As the silyl group, trimethylsilyl group, triethylsilyl group, tributylsilyl group, trihexylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, chloropropyldimethylsilyl group,
Silyl groups such as vinyldimethylsilyl group, isopropyldiethylsilyl group, diisopropyloctylsilyl group, phenyldimethylsilyl group, trimethylsilyl-substituted methyl group, trimethylsilyl-substituted ethyl group, trimethoxysilyl-substituted propyl group, trimethoxysilyl-substituted phenyl group, etc. Examples thereof include silyl-substituted alkyl groups.

As the aryl group, a phenyl group,
Examples thereof include an ethylphenyl group, a butylphenyl group, a nonylphenyl group, a naphthyl group, a butylnaphthyl group and a nonylnaphthyl group. The aryl group may be substituted with a hydroxyl group, halogen or the like, or may be substituted with the aryl group via an atom such as oxygen, sulfur or nitrogen. As the aryl substituted through oxygen, a phenoxyethyl group, a methoxyfell group, butoxyphenyl group and the like, as the aryl group substituted through sulfur, a phenylthioethyl group, a methyltheophenyl group,
Examples of the aryl group in which a butylthiophenyl group or the like is substituted via nitrogen include a dimethylaminophenyl group and a dibutylaminophenyl group.

In the general formula (I), Y ^{1 to} Y ⁴
As is each independently represent a fluorine-substituted alkyl group or fluorine-substituted oxaalkyl group having a C number to 14, and specific examples _{thereof, -CF 3, -C 2 F 5} , -C 3 F
_{7, -C 4 F 9, -C} 6 F 13, -C 7 F 15, -C 8 F 17, -C
F (CF ₃₎ [OCF ₂ (CF ₃₎ CF] MOC ₃ F ₇ (where, m = 0, 1, 2 or 3), and the like.

Specific examples of the phthalocyanine compound represented by the general formula (I) are shown in Table 1 [Table 1- (1)
To those shown in Table 1- (3)].

[0033]

[Table 1- (1)]

[0034]

[Table 1- (2)]

[0035]

[Table 1- (3)]

[0036]

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

Example 1 (Recordable High Density Recording Medium) A photopolymer was applied on a polymethylmethacrylate plate having a thickness of 1.2 μm, and the depth was 1000Å and the half width was 0.4 μm.
m and the track pitch of 1.4 μm, the compound No. The 1,2-dichloroethane solution of No. 3 was applied by spinner, and a recording layer having a thickness of 800 Å was provided to obtain a recording medium.

Examples 2 to 6 In Example 1, the compound No. Instead of 3
Compound No. 6, No. 8, No. 1
1, No. 14, No. Recording media of Examples 2 to 6 were obtained in the same manner as in Example 1 except that No. 19 was used.

Comparative Example 1 In Example 1, the compound No. A recording medium of Comparative Example 1 was obtained in the same manner as in Example 1 except that the compound represented by the following formula (II) was used instead of 3.

[Chemical 2] (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, light was incident from the substrate under the following recording conditions for recording, and then C / N and reflectance were measured at the recording position by reproducing light. did. 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 NA 0.5 Reproduction conditions: Scanning band width 30 KHz Reproduction power 0.25 to 0.3 mW

[0041]

[Table 2]

Example 7 (CD-R) Compound No. 1 in Table 1 was formed on a 1.2 mm thick injection-molded polycarbonate substrate having a guide groove with a depth of 1000Å, a half width of 0.45 μm and a track pitch of 1.6 μm. 2 of 4
-Ethoxyethanol / 1,2-dichloroethane / TH
A mixed solution of F [= 8 / 1.5 / 0.5 (weight ratio)] was applied by spinner, a recording layer having a thickness of 1800Å was provided, and Au was vacuum deposited on the recording layer to a thickness of 1500Å to form a reflective layer. did. Further, an acrylate-based photopolymer is applied onto it with a spinner, and UV-cured to form a protective layer,
A CD-R type recording medium was obtained.

Examples 8 to 11 In Example 7, the compound Nos. 4 instead of compound No. 4 in the same table. 8, No. 12, No. 1
6, No. Recording media of Examples 8 to 11 were obtained in the same manner as in Example 7 except that No. 18 was used.

Comparative Example 2 In Example 7, the compound No. A recording medium of Comparative Example 2 was obtained in the same manner as in Example 7, except that the phthalocyanine used in Comparative Example 1 was used instead of 4.

Comparative Example 3 In Example 7, the compound No. A recording medium of Comparative Example 3 was obtained in the same manner as in Example 7, except that the compound of the following formula (III) was used instead of 4.

[Chemical 3]

Comparative Example 4 In Comparative Example 3, 1 was added to the compound of the above formula (III).
A recording medium of Comparative Example 4 was obtained in the same manner as Comparative Example 3 except that a mixture containing 0% by weight of the nickel complex compound of the following formula (IV) was used.

[Chemical 4]

Using the recording media of Examples 7 to 11 and Comparative Examples 2 to 4, laser oscillation wavelength was 790 nm and linear velocity was 1.4 m.
The EFM signal was recorded under the recording condition of / sec, and the reflectance of the unrecorded portion and the 3T modulation degree at the optimum power were measured. The results are shown in Table 3.

[0048]

[Table 3]

[0049]

According to the optical recording medium of the present invention, since the phthalocyanine compound represented by the general formula (I) is contained in the recording layer, the wavelengths of 630 to 720n are obtained.
Since it has a high light absorption capacity and a high light reflection property for m, it can be applied to a pickup using a semiconductor laser of 630 to 720 nm capable of high density recording, and the current 770 to 830 n
It is possible to provide a high-density write-once recording medium having a recording density of 1.6 to 1.8 times that of the optical recording medium of m.

The optical recording medium of claim 2 comprises a phthalocyanine compound represented by the general formula (I) in the recording layer of a CD-R recording medium having a metal reflective layer laminated on the recording layer. As a result, a CD-R recording medium having a high refractive index at a wavelength of 770 to 830 nm and a high stability, and having a high reflectance and excellent storage stability and reproduction stability can be provided.

The optical recording medium of claim 3 has the formula (I) in which k = 1 = m = n = 1, the substitution position is 1 or 4 in the formula, and X ¹ R of the benzene ring. ^{1 to} X ⁴
The substituent other than R ⁴ or Y ^{1 to} Y ⁴ is a hydrogen atom or a halogen atom, and the recording layer contains a phthalocyanine compound. And the ability to prevent meetings was further improved,
In addition to the effect that the refractive index of the film can be further increased and the reflectance can be further improved, it is particularly suitable for a high refractive index CD-R recording medium.

The optical recording medium of claim 4 has the formula (I) in which k = l = m = n = 1, the substitution position is 2 or 3 in the formula, and X ¹ R of the benzene ring. ^{1 to} X ⁴
Since the substituents other than those substituted by R ⁴ or Y ^{1 to} Y ⁴ are those containing a phthalocyanine compound which is a hydrogen atom or a halogen atom in the recording layer, the wavelength can be increased without increasing the wavelength. Since the effect of being able to measure solubilization is added,
An excellent high-density addition type recording medium can be provided.

In the optical recording medium of claim 5, the recording layer is recorded and reproduced by laser light having a wavelength of 630 to 720 nm.
An additional recording medium having a recording density of 1.6 to 1.8 times higher than that of the optical recording medium of m is provided.

According to the optical recording medium of claim 6, the recording layer is recorded and reproduced by laser light having a wavelength of 770 to 830 nm.
A D-R recording medium is provided.

[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 Hard coat layer 6 Metal reflective layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI G11B 7/24 516 B41M 5/26 Y (56) References JP-A-6-15961 (JP, A) JP-A-6-309696 (JP, A) JP-A-5-96861 (JP, A) JP-A-5-1272 (JP, A) JP-A-6-41127 (JP, A) JP-A-5-295283 (JP, A) (JP-A-5) 58) Fields surveyed (Int.Cl. ⁷ , DB name) B41M 5/26 G11B 7/24 516 CAPLUS (STN) REGISTRY (STN) MARPAT (STN)

Claims (6)

(57) [Claims] 1. An optical recording medium in which a recording layer is provided on a substrate directly or via an undercoating layer and, if necessary, a protective layer is provided thereon, the following general formula ( An optical recording medium comprising at least one phthalocyanine compound represented by I). [Chemical 1] [In the formula, M, X ^{1 to} X ⁴ , R ^{1 to} R ⁴ , Y ^{1 to} Y ⁴ , k to n, and o to r each represent the following. M: 2 hydrogen atoms, a halogen atom or an oxygen atom a bivalent which may contain, trivalent or tetravalent metal atom, or - (OR ⁵⁾ s ^{group, - (OSiR 6 R 7 R} 8) t Group,-(OCO
R ⁹ ) u group or a metal atom which may have a — (OPOR ¹⁰ R ¹¹ ) v group, R ^{5 to} R ¹¹ : each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or Substituted or unsubstituted monovalent aromatic hydrocarbon group, s, t, u, v: an integer of 0 to 2, X ^{1 to} X ⁴ : each independently an oxygen atom or a sulfur atom, R ^{1 to} R ⁴ : each: Independently linear, branched or alicyclic alkyl group having 1 to 20 C's, optionally substituted, silyl group or optionally substituted aryl group, Y ^{1 to} Y ⁴ : independently C 1's ~ 14 fluorine-substituted alkyl group or fluorine-substituted oxaalkyl group, k, l, m, n: represents the number of substitution, an integer of 0-2, provided that all of k, l, m, n are 0 at the same time. O, p, q, r: represents the number of substitutions, an integer of 0 to 1, provided that o, p q, is not equal to 0 at the same time all of the r, should be noted that when the k + l + m + n + o + p + q + r <16,
The other substituent on the benzene ring is a hydrogen atom or a halogen atom. ) 2. The optical recording medium according to claim 1, which is provided with a protective layer.
In the body, a write-once compact disc type recording medium is provided, in which a metal reflection layer is provided between the recording layer and the protective layer, and a CD format signal is recorded .
Optical recording medium . 3. In the recording layer, k = 1 / m = n = 1 in the general formula (I), and the substitution position is 1 or 4
X ¹ R ^{1 to} X of the benzene ring
⁴ R ⁴ or a substituent other than those substituted with Y ^{1 to} Y ⁴ contains a compound which is a hydrogen atom or a halogen atom, and the absorption maximum wavelength (λmax) of the recording layer is 680 to 7
The optical recording medium according to claim 1 or 2, which has a thickness of 50 nm. 4. In the recording layer, k = 1 = m = n = 1 in the general formula (I), and the substitution position is 2 or 3.
X ¹ R ^{1 to} X of the benzene ring
^4. The optical recording medium according to claim 1, wherein the substituent other than ⁴ R ⁴ or Y ^{1 to} Y ⁴ is a hydrogen atom or a halogen atom. 5. The optical recording medium according to claim 1, wherein the recording layer is recorded and reproduced by laser light having a wavelength of 630 to 720 nm. 6. The optical recording medium according to claim 2, wherein the recording layer is recorded and reproduced by laser light having a wavelength of 770 to 830 nm.