JP2002188019A - Phthalocyanine compound and optical recording medium using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To supply a coloring matter capable of providing an optical recording medium having high sensitivity even in a high-speed recording and a high-density recording, having good recording properties and capable of forming a pit with high accuracy. SOLUTION: This phthalocyanine compound is represented by formula (1) in formula (1), M denotes two hydrogen atoms, a bivalent metal atom, a trivalent or tetravalent substituted metal atom or an oxymetal atom; and L1, L2, L3 and L4 denote each formula (a) or formula (b) independently [in formula (a) or formula (b), X1 and X2 denote each a 1-10C alkyl group, a 1-15C alkoxy group or a 1-10C alkylthio group; Y1 and Y2 denote each hydrogen atom, nitro group or a halogen atom; (A) denotes a residue of a metallic compound; and (B) denotes a group bonding the phthalocyanine compound and the compound of (A)] and at least one of the L1 to L4 denotes the formula (a)}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine compound which is useful in the field of optoelectronics such as an optical disk recording material, information recording, a display sensor and an optical card, and an optical disk formed by including the compound in a recording layer. And the like.

[0002]

2. Description of the Related Art Compact discs (hereinafter abbreviated as CDs)
As a write-once optical recording medium conforming to the standard, CD-R (CD-Re
It is known that cordable) has been proposed and developed,
Widely used for information recording.

[0003] Recording and reproduction of this CD-R is generally 78
A near-infrared semiconductor laser of 0 nm is used, and a signal is recorded in a heat mode on a recording layer made of an organic dye or the like on a substrate. That is, when the recording layer is irradiated with laser light, the organic dye generates heat by light absorption, and pits are formed in the recording layer by the generated heat. Signal recording is detected by a difference in reflectance between a portion where the pit is formed and a portion where the pit is not formed when the laser beam is irradiated. CD-R is compatible with CD players and CD-ROM players because it complies with CD standards such as Red Book and Orange Book, and has been provided at a low cost in recent years. It has been explosively and widely used for image storage and backup of personal computers and for music. Currently, with the improvement of the laser power of CD-R players, 12x speed, 16x
Double-speed recording has become possible, and what was originally required for 70 minutes or more per disk has been reduced to 5 minutes or less. In high-speed recording, pits are formed in a short time, so it is necessary to irradiate a high-power laser, but high-power laser irradiation imposes a heavy burden on the player,
In order to enable higher-speed recording, a dye that decomposes well even at low power, that is, a dye with high sensitivity is desired.

A technique using a phthalocyanine compound in a recording layer of a recording medium such as an optical disk or an optical card is disclosed in
1-1154888, 61-197280, 61-246091, 62-39286, 63-37991, 63-39388, etc., these phthalocyanines are widely known. In terms of sensitivity, refractive index, recording characteristics, etc., it was insufficient for optical recording media. An improved compound is described in JP-A-3-62878, but has a problem in recording characteristics at the time of writing with a laser beam, and is not yet practically sufficient. JP-A-4-214388 and JP-A-5-238150 disclose phthalocyanine compounds into which a fluorine atom has been introduced. However, introduction of a fluorine group improves adhesion to a substrate resin. Low sensitivity, described in JP-A-5-247363,
A compound in which a bromine atom is introduced into a phthalocyanine ring cannot be said to have sufficient performance in high-speed, high-density recording, and bromine and iodine groups are introduced into an alkyl group as disclosed in JP-A-7-90186. If so, the solubility decreases,
There was a problem that the solubility in the spin coat solvent at the time of preparing the recording medium was reduced.

[0005] WO 98/14520 describes a compound in which a phthalocyanine compound is modified with a substituent such as a formyl group or a carboxyl group. However, there is no description of a metal compound, and the sensitivity of the bonding of an organic group is low. The improvement was not enough.

[0006] Writing and reading to and from a CD-R are performed in 7
Since a laser beam near 80 nm is used, it is important to control the absorption coefficient and the refractive index in the vicinity of the laser oscillation wavelength and to form pits with high accuracy during writing. This is particularly important in high-speed recording and high-density recording. Therefore, it is necessary to develop a dye for an optical recording medium having high structural stability, a high refractive index for light near the laser oscillation wavelength, good decomposition characteristics, and high sensitivity. However, conventionally developed dyes, when used in recording media,
In particular, there was a problem that the sensitivity (C / N ratio, optimum recording power) and recording characteristics (jitter, deviation) of high-speed, high-density recording were not sufficient.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and has high sensitivity even in high-speed recording and high-density recording.
An object of the present invention is to provide a dye capable of providing an optical recording medium having good recording characteristics and capable of forming pits with high accuracy.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above-mentioned problems, and as a result, have found that the novel phthalocyanine compound of the present application has properties meeting the above-mentioned objects. That is, the present invention provides the following formula (1)

[0009]

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[In the formula (1), M represents two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal, and L ¹ , L ² , L ³ and L ⁴ are independently formulas (a), (b),

[0011]

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(In the formula (a) or (b), X ¹ and X ² are a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms. Represents a substituted or unsubstituted linear or branched alkylthio group having 1 to 10 carbon atoms,
Y ¹ and Y ^{2 each} represent a hydrogen atom, a nitro group or a halogen atom; (A) represents a metal compound residue; and (B) represents a group that binds the phthalocyanine compound to (A). ), And at least one of L ^{1 to} L ⁴ represents (a). ]

(B) is represented by the following formulas (B-1) to (B-
The phthalocyanine compound according to the above, which is selected from the bonding groups represented by 3).

[0014]

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In the formulas (B-1) to (B-3), D is -N
= CR^Five-, -NR⁶CO-, -CHR ⁷OCO-, -O
CO-¹~ R⁷Are each independently a hydrogen atom,
Or unsubstituted linear or branched alkyl having 1 to 10 carbon atoms
A substituted or unsubstituted aryl group having 6 to 15 carbon atoms
And Q¹, Q^TwoRepresents an oxygen or sulfur atom
You. ]

The phthalocyanine compound as described in the above, wherein the metal compound residue represented by (A) is a residue of a metallocene compound or a derivative thereof.

An optical recording medium comprising a substrate, a recording layer, and a reflective layer, wherein the recording layer contains the phthalocyanine compound described in any of the above.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalocyanine compound of the present invention has an absorption at 650-900 nm, has a high molecular extinction coefficient, and is excellent in long-term stability and durability. It is suitable for recording materials such as cards.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the formula (1), specific examples represented by X ¹ and X ² include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms. Linear or branched alkoxy group, substituted or unsubstituted carbon number 1
And 10 to 10 linear or branched alkylthio groups.

Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Heptyl group, octyl group, nonyl group, iso-propyl group,
sec-butyl group, t-butyl group, neo-pentyl group, 1,2-dimethylpropyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, 3-methyl-
1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group, 1-t-butyl-2-methylpropyl group, 2,4-dimethyl-3-propyl group, 2-methylpentyl group, 2 Unsubstituted alkyl group such as -ethylhexyl group, 2-chloroethyl group, 3-
Bromopropyl group, 2,2,3,3-tetrafluoropropyl group, alkyl group substituted with a halogeno group such as 1,1,1,3,3,3-hexafluoro-2-propyl group, 2-methoxy Ethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 1-ethoxy-2-propyl group, 3-methoxypropyl group, 3-methoxy-butyl group, 2,2-dimethyl-1,3-dioxolan-4- Alkoxy group substituted with alkoxy group such as methoxy group, 1,3-diethoxy-2-propoxy group, 2-dimethylaminoethyl group, 2-diethylaminoethyl group, 2-dibutylaminoethyl group, 2-diethylaminopropyl group, etc. And an alkyl group substituted with an alkylthio group such as a 1,3-diethylthio-2-propyl group.

Examples of the substituted or unsubstituted linear or branched alkoxy group having a total of 1 to 15 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyl and octyl. Oxy, nonyloxy, iso-propoxy, sec-butoxy, t-butoxy, neo-pentyloxy, 1,2-dimethylpropoxy, cyclohexyloxy, 1,3-dimethylbutoxy, 1-iso -Propylpropoxy group, 1,2-
Dimethylbutoxy group, 1,4-dimethylpentyloxy group,
2-methyl-1-iso-propylpropoxy group, 1-ethyl-3-methylbutoxy group, 3-methyl-1-iso-propylbutoxy group, 2-methyl-1-iso-propylbutoxy group, 1-t- Butyl-
2-methylpropoxy group, 2,4-dimethyl-3-propoxy group, 2-methylpentyloxy group, unsubstituted alkoxy group such as 2-ethylhexyloxy group, 2-chloroethoxy group,
3-bromopropoxy group, 2,2,3,3-tetrafluoropropoxy group, alkoxy group substituted with a halogeno group such as 1,1,1,3,3,3-hexafluoro-2-propoxy group, 1 , 1,1,3,3,
3-hexafluoro-2-phenyl-2-propoxy group, 1,1,1,
An alkoxy group substituted with a halogeno group and an aryl group such as 3,3,3-hexafluoro-2- (2,5-dimethyl) phenyl-2-propoxy group, a 2-methoxyethoxy group, a 2-ethoxyethoxy group, 2-butoxyethoxy group, 1-ethoxy-2-propoxy group, 3-methoxypropoxy group, 3-methoxybutoxy group, 2,2-dimethyl-1,3 dioxolan-4-methoxy group, 1,3
An alkoxy group substituted with an alkoxy group such as -diethoxy-2-propoxy group, 2-dimethylaminoethoxy group, 2-diethylaminoethoxy group, 2-dibutylaminoethoxy group, substituted with an amino group such as 2-diethylaminopropoxy group; And an alkoxy group substituted with an alkylthio group such as a 1,3-diethylthio-2-propoxy group.

Examples of the substituted or unsubstituted linear or branched alkylthio group having 1 to 10 carbon atoms include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio and the like. Group, iso-propylthio group, sec-
Butylthio group, t-butylthio group, neo-pentylthio group,
1,2-dimethylpropylthio group, cyclohexylthio group,
1,3-dimethylbutylthio group, 1-iso-propylpropylthio group, 1,2-dimethylbutylthio group, 1,4-dimethylpentylthio group, 2-methyl-1-iso-propylpropylthio group, 1
-Ethyl-3-methylbutylthio group, 3-methyl-1-iso-propylbutylthio group, 2-methyl-1-iso-propylbutylthio group, 1-t-butyl-2-methylpropylthio group, 2 , 4-dimethyl-3-propylthio group, 2-methylpentylthio group, 2-
An unsubstituted alkylthio group such as an ethylhexylthio group,
Chloroethylthio group, 3-bromopropylthio group, 2,2,3,
Alkylthio group substituted with a halogeno group such as 3-tetrafluoropropylthio group, 1,1,1,3,3,3-hexafluoro-2-propylthio group, 2-methoxyethylthio group, 2-ethoxyethylthio Group, 2-butoxyethylthio group, 1-ethoxy
2-propylthio group, 3-methoxy-propylthio group, 3-methoxybutylthio group, 2,2-dimethyl-1,3 dioxolan-4
-Methylthio group, alkylthio group substituted with an alkoxy group such as 1,3-diethoxy-2-propylthio group, 2-dimethylaminoethylthio group, 2-diethylaminoethylthio group,
2-dibutylaminoethylthio group, an alkylthio group substituted with an amino group such as a 2-diethylaminopropylthio group,
Examples thereof include an alkylthio group substituted with an alkylthio group such as a 1,3-diethylthio-2-propylthio group.

Specific examples of Y ¹ and Y ² include a hydrogen atom, a nitro group and a halogen atom such as a fluorine atom, a chlorine atom and an iodine atom, and are preferably a hydrogen atom, a chlorine atom and a bromine atom. Atoms.

Examples of the divalent metal represented by M include C
u (II), Zn (II), Fe (II), Co (II), Ni
(II), Ru (II), Rh (II), Pd (II), Pt
(II), Mn (II), Mg (II), Ti (II), Be
(II), Ca (II), Ba (II), Cd (II), Hg
(II), Pb (II), Sn (II), etc., monosubstituted trivalent metal
Examples of Al—Cl, Al—Br, Al—F, A
Il, Ga-Cl, Ga-F, Ga-I, Ga-B
r, In-Cl, In-Br, In-I, In-F, T
l-Cl, Tl-Br, Tl-I, Tl-F, Al-C
₆H_Five, Al-C₆H_Four(CH_Three), In-C₆H_Five, In-
C₆H_Four(CH_Three), In-C_TenH₇, Mn (OH), Mn
(OC₆H_Five), Mn [OSi (CH_Three)_Three], FeCl,
RuCl and the like. As an example of a disubstituted tetravalent metal
CrCr_Two, SiCl_Two, SiBr_Two, SiF_Two, S
iI_Two, ZrCl_Two, GeCl_Two, GeBr_Two, GeI_Two,
GeF_Two, SnCl_Two, SnBr_Two, SnI_Two, SnF_Two,
TiCl_Two, TiBr_Two, TiF_Two, Si (OH)_Two, Ge
(OH)_Two, Zr (OH)_Two, Mn (OH)_Two, Sn (O
H) _Two, TiR_Two, CrR_Two, SiR_Two, SnR_Two, GeR_Two
[R is an alkyl group, a phenyl group, a naphthyl group and
Represents a derivative], Si (OR ')_Two, Sn (O
R ')_Two, Ge (OR ')_Two, Ti (OR ')_Two, Cr
(OR ')_Two[R ′ is an alkyl group, an alkylcarbonyl
Group, phenyl group, naphthyl group, trialkylsilyl group,
Represents a dialkylalkoxysilyl group and its derivatives
Do]. Examples of oxymetals include V
O, MnO, TiO and the like can be mentioned.

The bonding group represented by (B) is not particularly limited as long as it can bond the phthalocyanine compound and the metal compound residue (A).
1) to (B-3)

[0026]

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In the formulas (B-1) to (B-3), D is -N
= CR^Five-, -NR⁶CO-, -CHR ⁷OCO-, -O
CO-¹~ R⁷Are each independently a hydrogen atom,
Or unsubstituted linear or branched alkyl having 1 to 10 carbon atoms
A substituted or unsubstituted aryl group having 6 to 15 carbon atoms
And Q¹, Q^TwoRepresents an oxygen or sulfur atom
You. ]

Specific examples of the substituents represented by R ^{1 to} R ⁷ include a substituted or unsubstituted linear or branched alkyl group having a total of 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. , Butyl, pentyl, hexyl, heptyl, octyl, nonyl, iso-propyl, sec-butyl, t-butyl, neo-pentyl, 1,2-dimethylpropyl, cyclohexyl, 1,3-dimethylbutyl group, 1-
iso-propylpropyl group, 1,2-dimethylbutyl group, 1,4-
Dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group, 1
-t-butyl-2-methylpropyl group, alkyl groups such as 2,4-dimethyl-3-propyl group, trifluoromethyl group, 2,2,3,
3-tetrafluoropropyl group, an alkyl group substituted with a halogeno group such as a 2-chloroethyl group,

Examples of the substituted or unsubstituted aryl group having a total of 6 to 15 carbon atoms include an unsubstituted aryl group such as a phenyl group, a naphthyl group and a phenanthryl group, a 2-methylphenyl group,
4-methylphenyl group, 2,3--dimethylphenyl group, 2,6-
Dimethylphenyl group, 2,4-dimethylphenyl group, 2,4-diisopropylphenyl group, 2,6-ditertbutylphenyl group,
3,4--dimethylphenyl group, 3,6-dimethylphenyl group,
2,3,4-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, cyclohexylphenyl group, octylphenyl group, 2-methyl-1-naphthyl group , 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, alkyl group such as 2-ethyl-1-naphthyl group Substituted aryl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 2,3-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,6-dimethoxyphenyl group, 2,3,4-trimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, octyloxyphenyl group Etc. Aryl group and the like substituted with alkoxy groups.

As the metal compound residue represented by (A), any residue of a compound containing a metal may be used, but a metallocene compound residue is preferable. As a specific example of such a compound containing a metal, Fe (C
p) ₂ (where Cp represents a cyclopentadienyl group; the same applies hereinafter), Co (Cp) ₂ , Ni (Cp) ₂ , Ru (C
p) ₂ , Os (Cp) ₂ , Mn (Cp) ₂ , Cr (C
p) ₂ , W (Cp) ₂ , V (Cp) ₂ , Sc (Cp) ₃ , Y
(Cp) ₃ , La (Cp) ₃ , Ce (Cp) ₃ , Pr (C
p) ₃ , Nd (Cp) ₃ , Sm (Cp) ₃ , Gd (C
p) ₃ , Er (Cp) ₃ , Tm (Cp) ₃ , Yb (C
p) ₃ , metallocene compounds such as cyclopentadienyl manganocentricarbonyl, titanocene diphenoxide, bis (cyclopentadienyl) bis (2,6-difluoro-
3- (1H-pyrrol-1-yl) phenyltitanium, metallocene compounds having a substituted metal such as cyclopentadienyl manganocentricarbonyl and the like, and these metallocene compounds are represented by an alkyl group, an aryl group, and an acyl group. It may be substituted.

The bond between the bonding group and the metallocene compound includes a bond with a cyclopentadienyl ring, a direct bond with a metal, and the like, and for example, a bond with a cyclopentadienyl ring.

The compounds represented by the general formula (1) include, for example, the following (i) to (iii) (Pc is a phthalocyanine compound, and the group described in the β-position of Pc is bonded. M ′ is a metallocene The metal atom and Hal represent halogen.), But the invention is not limited thereto.

For example, (i) a method of synthesizing a compound (III) by dehydrating and condensing a formyl phthalocyanine compound (I) and a metallocene aldehyde (II) with hydrazine;

[0034]

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(Ii) A compound (VI) is synthesized by etherification using a halogen-containing phthalocyanine compound (IV) and hydroxymethylphenol (V), and then esterified with a metallocenecarboxylic acid (VII) to give a compound (VIII) How to synthesize

[0036]

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(Iii) Aminophenol (IX) is directly bound to metallocene compound (X) by the method described in J. Am. Chem. Soc., 77, 3012 (1955) to synthesize compound (XI). A method of etherifying with a phthalocyanine compound to synthesize compound (XII).

[0038]

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The phthalocyanine compound has structural isomers in a known manner, and the resulting compound is a mixture thereof. Further, in the present application, since a metal-based compound is bonded, a large number of structural isomers are generated, and the compound is obtained as a mixture of compounds having different substitution numbers. The compound described in the present application is a mixture mainly containing the compound represented by the structural formula, and is not limited to the compound represented by the structural formula.

Table 1 shows specific examples of the phthalocyanine compound represented by the general formula (1) of the present invention.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

(A-1): Fe (Cp) ₂ (A-2): Cr (Cp) ₂ (A-3):

[0046]

Embedded image (A-4): Ru (Cp) ₂ (A-5): La (Cp) ₃ (A-6): Sc (Cp) ₃ (A-7): Er (Cp) ₃ (A-8): Y (Cp) ₃ (A-9): Ni (Cp) ₂

The optical recording medium refers to both a read-only optical read-only medium on which information is recorded in advance and an optical recording medium capable of recording and reproducing information. Here, as an example, an optical recording medium capable of recording and reproducing the latter information, in particular, an optical recording medium having a recording layer and a reflective layer on a substrate will be described.

As a material of the substrate, basically, it is sufficient that the substrate is transparent at the wavelength of the recording light and the reproducing light. For example, polymer materials such as acrylic resins such as polycarbonate resin, vinyl chloride resin and polymethyl methacrylate, polystyrene resins and epoxy resins, and inorganic materials such as glass are used.
These substrate materials are formed into a disk shape by injection molding or the like. If necessary, guide grooves or pits may be formed on the substrate surface. Such guide grooves and pits
It is desirable to apply it at the time of molding the substrate, but it can also be applied using an ultraviolet curable resin layer on the substrate.

In the present invention, a recording layer is provided on a substrate, and the recording layer of the present invention has a λmax of 650 nm to 900 nm.
It contains a phthalocyanine compound represented by the general formula (1) existing near nm. Above all, an appropriate optical constant (optical constant is expressed by a complex refractive index (n + ki) for a recording and reproducing laser wavelength near 780 nm. In the formula, n and k correspond to a real part n and an imaginary part k. Here, n is a refractive index, and k is an extinction coefficient.)

In general, an organic dye is characterized in that the refractive index n and the extinction coefficient k greatly change with respect to the wavelength λ. n is 1.
If the value is less than 8, it becomes difficult to obtain the reflectance and the signal modulation degree necessary for accurate signal reading. Even if k exceeds 0.40, the reflectance is reduced and a good reproduced signal cannot be obtained. In some cases, the signal is easily changed by the reproduction light and is not suitable for practical use. In consideration of this feature, by selecting an organic dye having a preferable optical constant at a target laser wavelength and forming a recording layer, a medium having high reflectance and high sensitivity can be obtained. .

The phthalocyanine compound represented by the general formula (1) used in the present invention has a high extinction coefficient and the absorption wavelength range can be arbitrarily selected by selecting a central metal and a substituent. , Optical constants required for the recording layer (n is 1.8 or more, and k is 0.04 to 0.4).
40, preferably an extremely useful compound satisfying n of 2.0 or more and k of 0.04 to 0.20).

Further, if necessary, a binder, a leveling agent, an antifoaming agent and the like can be used in combination. Preferred binders include polyvinyl alcohol, polyvinylpyrrolidone, nitrocellulose, cellulose acetate,
Ketone resin, acrylic resin, polystyrene resin, urethane resin, polyvinyl butyral, polycarbonate, polyolefin and the like can be mentioned.

When the recording layer is formed on the substrate, in order to improve the solvent resistance, the reflectance, the recording sensitivity, etc. of the substrate,
A layer made of an inorganic substance or a polymer may be provided on the substrate.

Here, the content of the phthalocyanine compound represented by the general formula (1) in the recording layer is 30% by mass or more, preferably 60% by mass or more. In addition, substantially 1
It is also preferable that the amount is 00% by mass.

The method for providing the recording layer includes, for example, a coating method such as a spin coating method, a spray method, a casting method, and a dipping method, a sputtering method, a chemical vapor deposition method, and a vacuum vapor deposition method. Is preferred.

When a coating method such as a spin coating method is used, the phthalocyanine compound represented by the general formula (1)
A coating solution dissolved or dispersed in a solvent so as to have a concentration of ４０40% by mass, preferably 3-30% by mass is used. At this time, it is preferable to select a solvent that does not damage the substrate. For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, and tetrafluoropropanol, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, and dimethylcyclohexane Aliphatic or alicyclic hydrocarbon solvents such as, toluene, xylene, aromatic hydrocarbon solvents such as benzene, carbon tetrachloride, chloroform, tetrachloroethane, halogenated hydrocarbon solvents such as dibromoethane, diethyl ether, Ether solvents such as dibutyl ether, diisopropyl ether, dioxane,
Examples include ketone solvents such as acetone and 3-hydroxy-3-methyl-2-butanone, ester solvents such as ethyl acetate and methyl lactate, and water. These may be used alone or in combination.

If necessary, the dye of the recording layer may be dispersed in a polymer thin film or the like.

When a solvent that does not damage the substrate cannot be selected, a sputtering method, a chemical vapor deposition method, a vacuum vapor deposition method, or the like is effective.

The thickness of the dye layer is not particularly limited, but is preferably 50 nm to 300 nm. If the thickness of the dye layer is less than 50 nm, recording cannot be performed due to large thermal diffusion, or a recording signal will be distorted and the signal amplitude will be small. On the other hand, when the film thickness is larger than 300 nm, the reflectivity decreases and the reproduction signal characteristics deteriorate.

Next, on the recording layer, preferably 50 nm
A reflective layer having a thickness of 300 nm is formed. As a material of the reflection layer, a material having sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Ag, Cu, Ti, Cr, Ni, P
The metals t, Ta, Cr and Pd can be used alone or as an alloy. Among them, Au, Al,
Ag has a high reflectance and is suitable as a material for the reflective layer. In addition, the following may be included. For example, M
g, Se, Hf, V, Nb, Ru, W, Mn, Re, F
e, Co, Rh, Ir, Zn, Cd, Ga, In, S
Metals and metalloids such as i, Ge, Te, Pb, Po, Sn, Bi and the like can be mentioned. Further, those containing Au as a main component are preferable because a reflection layer having high reflectance can be easily obtained. Here, the main component means a component having a content of 50% or more. It is also possible to form a multilayer film by alternately stacking low-refractive-index thin films and high-refractive-index thin films with a material other than a metal, and use it as a reflective layer.

As a method of forming the reflection layer, for example,
Examples include a sputtering method, an ion plating method, a chemical vapor deposition method, and a vacuum vapor deposition method. In addition, a known inorganic or organic intermediate layer or adhesive layer may be provided on the substrate or below the reflective layer to improve the reflectance, the recording characteristics, and the adhesion.

The material of the protective layer provided on the reflective layer is not particularly limited as long as it protects the reflective layer from external force, and is selected from organic and inorganic substances.
Examples of the organic substance include a thermoplastic resin, a thermosetting resin, an electron beam curable resin, and an ultraviolet curable resin. As the inorganic substance, SiO ₂ , Si ₃ N ₄ ,
MgF ₂ , SnO _{2 and the} like can be mentioned. A thermoplastic resin, a thermosetting resin, or the like can be formed by dissolving in a suitable solvent, applying a coating solution, and drying. The ultraviolet curable resin can be formed by preparing a coating solution as it is or by dissolving it in an appropriate solvent, applying the coating solution, and irradiating ultraviolet rays to cure the resin. As the ultraviolet curable resin, for example, acrylate resins such as urethane acrylate, epoxy acrylate, and polyester acrylate can be used.
These materials may be used alone or as a mixture,
Not only a single layer but also a multilayer film may be used.

As a method for forming the protective layer, a coating method such as a spin coating method or a casting method, a sputtering method or a chemical vapor deposition method is used as in the case of the recording layer. Of these, the spin coating method is preferable.

The thickness of the protective layer is generally 0.1 μm to 1 μm.
In the present invention, the range is from 3 μm to
It is 30 μm, more preferably 5 μm to 20 μm.

A label or the like can be further printed on the protective layer. Further, a means such as bonding a protective sheet or a substrate to the reflective layer surface, or bonding two optical recording media with the reflective layer surfaces facing each other and facing each other may be used. Further, an ultraviolet curable resin, an inorganic thin film, or the like may be formed on the mirror surface of the substrate to protect the surface and prevent adhesion of dust and the like.

[0066]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.

Example 1 1.58 g (1.0 mm) of a phthalocyanine compound represented by the following structural formula (2) described in JP-A-3-62878.
ol), 0.33 g (1.2 mmol) of p-ferrocene phenol represented by the following structural formula (3) and potassium carbonate 0.21 synthesized by the method described in J. Am. Chem., 77, 3012 (1955).
g (1.5 mmol) and 20 ml of dimethylimidazolidinium (hereinafter abbreviated as DMI) were mixed and reacted at 160 ° C. for 4 hours. After cooling to room temperature, the mixture was discharged into methanol, the precipitated solid was separated, purified by column chromatography, and 0.84 g (0.46 mol) of a phthalocyanine compound represented by the following structural formula (1-1) (yield) 46%)
I got it.

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Absorption wavelength: λmax = 721 nm Gram extinction coefficient: εg = 135,000 (solvent: toluene) Elemental analysis: C ₈₈ H ₁₀₁ Cl ₇ FeN ₈ O ₉ Pd Calculated value (%) C: 57.91% H : 5.58%
N: 6.14% Analysis value (%) C: 57.78% H: 5.41%
N: 6.29%

Example 2 1.39 g (5 mmol) of p-ferrocene phenol (3)
l) and 0.83 g (6.0 mmol) of potassium carbonate, except that the following structural formula (1-
1.63 g of the phthalocyanine compound represented by 3)
(0.64 mol) (64% yield).

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Embedded image Absorption wavelength: λmax = 724 nm Gram extinction coefficient: εg = 96,000 (solvent: toluene) Elemental analysis: C ₁₃₆ H ₁₄₀ Cl ₄ Fe ₄ N ₈ O ₁₂ Pd Calculated (%) C: 64.05% H: 5.53%
N: 4.39% Analysis value (%) C: 63.78% H: 5.41%
N: 4.29%

Example 3 Phthalocyanine compound (2) 1.5 used in Example 1
8 g (1.0 mmol), m-aminophenol 0.1
3 g (1.19 mmol), potassium carbonate 0.21 g
(1.5 mmol) and 20 ml of DMI,
The reaction was performed at 4 ° C. for 4 hours. After cooling to room temperature, the mixture was discharged into methanol, the precipitated solid was separated, and 1.41 g (0.85 mmol) of a mixture containing the m-aminophenoxyphthalocyanine compound represented by the following structural formula (4) was obtained (yield: 85).
%), Further mixed with 1.16 g (0.7 mmol) of this m-aminophenoxyphthalocyanine compound (4), 20 ml of toluene and 0.1 ml of pyridine, and further mixed with ferrocenecarboxylic acid (manufactured by Aldrich). .Or
0.2 g (0.80 mmol) of ferrocenecarboxylic acid chloride synthesized according to g. Chem., 24, 280 (1959) was added and reacted at room temperature for 3 hours. After adding water, the mixture was extracted, washed with water, toluene was distilled off, and the residue was purified by column chromatography. 0.86 g (0.46 mmol) of phthalocyanine compound represented by the following structural formula (1-14) (yield Rate 66%).

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Absorption wavelength: λmax = 721.5 nm Gram extinction coefficient: εg = 133,000 (solvent: toluene) Elemental analysis: C ₈₉ H ₁₀₂ Cl ₇ FeN ₉ O ₁₀ Pd Calculated value (%) C: 57.22 % H: 5.50%
N: 6.75% Analysis value (%) C: 57.44% H: 5.38%
N: 6.68%

Example 4 A phthalocyanine compound 1.6 represented by the following structural formula (5), which was synthesized by the method described in JP-A-3-62878.
7 g (1.0 mmol), p-aminothiophenol 0.15 g (1.2 mmol), potassium carbonate 0.21
g (1.5 mmol) and 20 ml of DMI.
The reaction was performed at 0 ° C. for 5 hours. After cooling to room temperature, the mixture was discharged into methanol, and the precipitated solid was separated, and 1.39 g (0.79 mmol) of a p-aminophenylthioxyphthalocyanine compound represented by the following structural formula (6) (79% yield) was obtained.
1.23 g (0.7 mmol) of this p-aminophenylthioxyphthalocyanine compound (6),
The phthalocyanine compound represented by the following structural formula (1-18) was amidated in the same manner as in Example 3 by using
8 g (0.50 mmol) (66% yield) was obtained.

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Absorption wavelength: λmax = 725 nm Gram extinction coefficient: εg = 132,000 (solvent: toluene) Elemental analysis: C ₈₉ H ₁₀₂ Cl ₇ FeN ₉ O ₁₇ SZn Calculated value (%) C: 54.23% H : 5.22%
N: 6.39% Analysis value (%) C: 54.54% H: 5.32%
N: 6.48%

Example 5 Phthalocyanine compound (2) 1.5 used in Example 1
8 g (1.0 mmol) was mixed with 0.15 g (1.21 mmol) of 3-hydroxymethylphenol, 0.21 g (1.5 mmol) of potassium carbonate, and 20 ml of DMI, and reacted at 140 ° C. for 4 hours. After cooling to room temperature, the mixture was discharged into methanol, the precipitated solid was separated, and 1.39 g (0.83 mmol) of a 3- (hydroxymethyl) phenoxyphthalocyanine compound represented by the following structural formula (7) was obtained.
l) (83% yield), and the 3- (hydroxymethyl) phenoxyphthalocyanine compound (7) 1.1
7 g (0.7 mmol) of ferrocenecarboxylic acid chloride 0.2 g (0.8 mmol) in the same manner as in Example 3.
l) to give 1.07 g (0.57 g) of a phthalocyanine compound represented by the following structural formula (1-28).
mmol) (81% yield).

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Absorption wavelength: λmax = 721.5 nm Gram extinction coefficient: εg = 102,000 (solvent: toluene) Elemental analysis: C ₉₀ H ₁₀₃ Cl ₇ FeN ₈ O ₁₁ Pd Calculated value (%) C: 57.40 % H: 5.51%
N: 5.95% Analysis value (%) C: 57.66% H: 5.62%
N: 5.75%

Example 6 Dry dimethylformamide (hereinafter abbreviated as DMF) 4.38
g (60 mmol) under water cooling under phosphorus oxychloride 9.2.
g (60 mmol) was added dropwise, and the mixture was stirred at room temperature.
An ier reagent was prepared, and a solution of 12.65 g (10 mmol) of a phthalocyanine compound represented by the following structural formula (8), synthesized in accordance with the method described in JP-A-3-62878, in 100 ml of chlorobenzene was added and reacted at 80-90 ° C. for 3 hours. I let it. After completion of the reaction, after cooling to room temperature, an aqueous solution of sodium acetate was added, and the mixture was extracted with chloroform,
After washing with water, the extract is dried over anhydrous sodium sulfate, the solvent is distilled off, the residue is purified by column chromatography, and the formyl phthalocyanine compound 9.3 represented by the following structural formula (9) is obtained.
1 g (7.2 mmol) (72% yield) was obtained.

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On the other hand, 4.38 g of dry DMF (60 mm
l) was added with 9.2 g (60 mmol) of phosphorus oxychloride under water cooling.
After l) was added dropwise, the mixture was stirred at room temperature to prepare a Vilsmeier reagent, and a solution of 6.94 g (30 mmol) of ruthenocene in 50 ml of chlorobenzene was added and reacted at 80 to 90 ° C for 10 hours. After completion of the reaction, after cooling to room temperature, an aqueous sodium acetate solution was added, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off.
Purified by column chromatography, the following structural formula (1
4.82 g of formylruthenocene (18.
6 mmol) (62% yield).

19.5 g of hydrazine monohydrate (0.39
mol), formyl ruthenocene (1.01 g, 3.9 g) was obtained.
(mmol) in methanol at room temperature to react. Drained into water, the precipitated solid is filtered and washed with water,
0.79 g (2.9 mmol) of ruthenocene aldazone represented by the following structural formula (11) was obtained (yield 74%).

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Formyl phthalocyanine compound (9) 3.
After dissolving 88 g (3.0 mmol) in 50 ml of toluene, 1.64 g of ruthenocene aldazone (11) was dissolved.
(6.0 mmol) was added and reacted at room temperature. After distilling off the solvent, the residue was purified by column chromatography, and 3.72 g of a mixture containing a phthalocyanine compound represented by the following structural formula (1-37) (2 .4 mol) (yield 80
%).

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Absorption wavelength: λmax = 739 nm Gram extinction coefficient: εg = 124,000 (solvent: toluene) Elemental analysis: C ₈₄ H ₁₀₆ CuN ₁₀ O ₈ Ru Calculated (%) C: 65.16% H: 6 .90%
N: 9.05% Analytical value (%) C: 65.08% H: 6.72%
N: 8.88%

Example 7 A dye solution was prepared by dissolving 0.2 g of the phthalocyanine compound (1-1) described in Example 1 in 10 ml of dimethylcyclohexane. The substrate is made of polycarbonate resin and has a continuous guide groove (track pitch: 1.6 μm), a diameter of 120 mm and a thickness of 1.2 mm.
mm disk-shaped thing was used.

The dye solution is applied onto the substrate at a rotational speed of 1000
Spin coating was performed at 1500 rpm and dried at 70 ° C. for 3 hours to form a recording layer.

Au was sputtered on the recording layer using a sputtering apparatus (CDI-900, manufactured by Balzers) to form a reflective layer having a thickness of 100 nm. Argon gas was used as a sputtering gas. The sputtering conditions were as follows: a sputtering power of 2.5 kW and a sputtering gas pressure of 1.33 Pa (1.0 × 1
0 ^-2 Torr).

Further, an ultraviolet curable resin SD-
After spin-coating 1700 (manufactured by Dainippon Ink and Chemicals, Inc.), an ultraviolet ray was irradiated to form a protective layer having a thickness of 6 μm, thereby producing an optical recording medium.

An optical disk evaluation device (DDU- manufactured by Pulstec Industrial Co., Ltd.) equipped with a semiconductor laser head having a wavelength of 780 nm and a numerical aperture of a lens of 0.5 is mounted on the obtained optical recording medium.
1000) at a linear speed of 14.4 m / s
FM signals were recorded at a laser power of 18-20 mW. The signal was reproduced using the evaluation device, and the jitter, deviation and error rate of the shortest pit (length 0.8 μm) were measured. As a result, the laser power was 18 mW, and the jitter was 20 ns, the deviation was 10 ns, and the error rate was 100 or less. Value.

Comparative Example 1 A phthalocyanine compound represented by the following structural formula (12) was prepared in the same manner as in Example 7 to prepare a CD-R medium, and evaluated in the same manner. When the laser power was 18 mW, the jitter was 56% and the deviation was 56%. 52 ns, error rate 4
It was not less than 50, which was not sufficient.

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Comparative Example 2 A phthalocyanine compound represented by the following structural formula (13) described in WO98014520 was converted into C
When a DR medium was prepared and evaluated in the same manner, when the laser power was 18 mW, the jitter was 78 ns, the deviation was 70 ns, and the error rate was 1250 or more, and the characteristics were not sufficient.

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Examples 8 to 25 CD-R media were prepared in the same manner as in Example 7 except that the phthalocyanine compounds shown in Table 1 were used, and recording was performed with a laser power of 18 mW. 8μ
m) Jitter, deviation and error rate were evaluated. The results all showed good values as described in Table-2.・ Evaluation of jitter: ○: 35 ns or less, ×: 35 ns
It is shown above.・ Evaluation of deviation: ○ is 40 ns or less, × 40
ns or more.・ Evaluation of error rate: ○ is less than 220, × is 220
It is shown above.

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[Table 5]

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The phthalocyanine compound of the present invention is a phthalocyanine compound to which a metal compound is bonded.
The compound of the present invention has good decomposition characteristics due to the binding of the metal-based compound, and has a high absorption coefficient and a high refractive index near 780 nm, and particularly has high sensitivity at high speed and high density recording (optimal recording power, etc.) and recording. Improved characteristics (jitter, deviation).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07F 17/02 B41M 5/26 Y (72) Inventor Shinichi Nakagawa 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Denmi Misawa 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.F-term (reference) 2H111 FA01 FB45 4H050 AA01 AB92 WB11 WB21 5D029 JA04

Claims (4)

[Claims] 1. A phthalocyanine compound represented by the following formula (1). Embedded image [In the formula (1), M represents two hydrogen atoms, a divalent metal atom,
Represents a trivalent or tetravalent substituted metal atom or an oxymetal, and L ¹ , L ² , L ³ and L ⁴ are each independently a group represented by the formula (a), the formula (b) or (In the formula (a) or the formula (b), X ¹ and X ² are a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms,
Represents a substituted or unsubstituted linear or branched alkoxy group having 1 to 15 carbon atoms, a substituted or unsubstituted linear or branched alkylthio group having 1 to 10 carbon atoms, and Y ¹ and Y ² represent a hydrogen atom, nitro Represents a group or a halogen atom, (A) represents a metal compound residue, and (B) represents a group that binds the phthalocyanine compound to (A). ), And L ^{1 to} L ⁴
At least one of them represents (a). ] 2. The method according to claim 1, wherein (B) is the following formula (B-1) to (B-
2. The lid according to claim 1, which is selected from the bonding groups represented by 3).
Russian compound. Embedded image[In the formulas (B-1) to (B-3), D is -N = CR^Five−,
-NR⁶CO-, -CHR ⁷OCO- and -OCO-
Then R¹~ R⁷Are each independently a hydrogen atom, substituted or unsubstituted
A linear or branched alkyl group having 1 to 10 carbon atoms,
Or an unsubstituted aryl group having 6 to 15 carbon atoms;
¹, Q^TwoRepresents an oxygen atom or a sulfur atom. ] 3. The phthalocyanine compound according to claim 1, wherein the residue of the metal compound represented by (A) is a residue of a metallocene compound or a derivative thereof. 4. An optical recording medium comprising a substrate, a recording layer and a reflective layer, wherein the phthalocyanine compound according to claim 1 is contained in the recording layer.