JPH07118551A - New fluorophthalocyanine compound, its production, near-infrared-absorbing material containing same, and optical recording medium containing same - Google Patents

Abstract

PURPOSE:To obtain a material an absorption in a near-infrared region of 650-800nm and excellent in solvent solubility and lightfastness by reacting a 2,4,5,6-tetrafluorophthalonitrile compound with a fluorophthalonitrile compound and a metal compound. CONSTITUTION:3,4,5,6-Tetrafluorophthalonitrile is reacted with 0.25mol, per mol of the phthalonitrile, at least one compound selected from among fluorophthalonitriles of formula I and a metal oxide, a metal halide or an organic acid metal salt of formula II to obtain the purpose compound of formula III. IN the formulas, X is a group of formula IV (wherein A is 1-8C alkyl; Z is H, etc.; and p is 0-2), etc.; Me is a metal; Y is oxygen, halogen or an organic acid group; t is 1-3; X has a value determined by the atomic valence of Me or Y; X<1>, X<2>, X<3> and X<4> are each a group of formula IV, etc., and is at the position beta of the corresponding benzene ring; a, b, c and d are each 0-2; and the sum total of a, b, c and d is 1-3; F is fluorine; and M is a metal, a metal oxide, a metal hydroxide or a metal halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing phthalocyanine compound, a method for producing the same, a near-infrared absorbing material and an optical recording medium containing this fluorine-containing phthalocyanine compound.

The fluorinated phthalocyanine compound of the present invention has absorption in the near infrared region of 650 to 800 nm, is excellent in solubility in a solvent, and is also excellent in light resistance originally possessed by phthalocyanine. Therefore, near-infrared absorbing dyes for writing or reading in optical recording media using semiconductor lasers, liquid crystal displays, optical character readers, etc .; near-infrared photosensitizers; thermal transfer, thermal paper, thermal stencil, etc. Photothermal conversion agent; near-infrared absorption filter; eye strain prevention agent; photoconductive material; photosensitive dye for tumor treatment that absorbs light in the long wavelength range with good tissue permeability; heat ray shielding agent for automobiles, building materials, etc. Used.

In particular, optical recording media such as compact disks, laser disks, optical memory disks, optical cards,
Among them, especially PHOTO-CD compatible with compact disk (CD) that records and reproduces information by laser light.
Alternatively, it exhibits an excellent effect when used as a compact disc-ROM (CD-ROM) compatible device.
Furthermore, when used as a visible absorption material having visible absorption, for example, for color separation filters used in image pickup tubes, liquid crystal display elements, color cathode ray tube selective absorption filters, color toners, inkjet inks, tampering prevention barcode inks, etc. It has excellent effects.

[0004]

2. Description of the Related Art In recent years, a system using a semiconductor laser as a light source for writing or reading in an optical recording medium such as a compact disc, a laser disc, an optical memory disc, an optical card, a liquid crystal display device, and an optical character reader. Is actively developing. Especially the CD,
PHOTO-CDs or CD-ROMs have been used in large quantities as large-capacity, high-speed access digital recording media for storing and reproducing sounds, images, code data and the like.
All of these systems require so-called near-infrared absorbing dyes that are sensitive to semiconductor lasers, and those having excellent characteristics are required. In addition, photoconductive materials, near-infrared absorption filters, eye strain inhibitors, heat-transfer / heat-sensitive paper, photothermal converters such as heat-sensitive stencil, near-infrared photosensitizers, long-wavelength light with good tissue permeability. There is an increasing demand for development of a so-called near-infrared absorbing dye, which is a substance that absorbs near-infrared rays, such as a photosensitive dye for tumor treatment having absorption, a heat ray shielding agent used for automobiles, building materials and the like.

Among these near infrared absorbing dyes, light, heat,
For phthalocyanine compounds that are stable to temperature and have excellent robustness, many studies have been conducted to control the absorption wavelength required depending on the application and to dissolve it in the solvent required depending on the application. Has been done.

That is, with the diversification of devices in recent years,
Further, dyes having various absorption characteristics are required depending on the use, but it is difficult to control the absorption wavelength of the phthalocyanine compound. Also, in practice, a method of forming a thin film of a dye without using a complicated process such as vapor deposition or dispersion in a resin, using a solvent that does not attack the substrate used for the device, or solubility in the resin used together Therefore, most of the phthalocyanine-based compounds are insoluble in the solvent, although dyes that are soluble in various solvents at high concentrations are required according to their respective uses.

When used in a write-once type optical recording medium such as a compact disc, a laser disc, an optical memory disc and an optical card, the dye itself has a particularly high reflectance in addition to the above-mentioned characteristics such as solubility, and the optical property. Although it is required that the dye decomposes as quickly as possible with respect to the heat generated upon absorption of phthalocyanine, the fact is that no phthalocyanine-based compound satisfying them has been proposed.

Under these circumstances, the dye practically used for optical recording media is usually a cyanine dye. However, since the cyanine dye has poor light resistance and thus has a limited range of applications, there is a demand for a phthalocyanine compound having good light resistance, which satisfies the above-mentioned characteristics.

As a phthalocyanine compound having a practical solubility, JP-A-61-223058 discloses 3,
Although 6-octaalkoxy phthalocyanine has been proposed, this phthalocyanine compound has problems that the control of the absorption wavelength is limited to the low wavelength side, and the manufacturing process is complicated and cannot be manufactured at low cost.

JP-A-60-209583, JP-A-61-161
No. 152685, JP-A-63-308073 and JP-A-64-62361 each disclose a phthalocyanine compound in which a phthalocyanine skeleton is substituted with a large number of thioether groups to improve solubility and lengthen absorption wavelength. Is disclosed. Among them, JP-A-60-209583 and JP-A-61-252685 disclose synthetic examples in which a thioether group is introduced at the phthalocyanine skeleton, particularly at the 3,6-position. The method is to heat a phthalocyanine compound having a chlorine atom at the 3,6-position (α-position) of a phthalocyanine skeleton and an organic thiol compound in a quinoline solvent in the presence of KOH to have a thioether group at the 3,6-position. It is to obtain a phthalocyanine compound. However, in all cases, the yield is about 20 to 30%, there is a problem in production efficiency, the solubility is still insufficient, and the absorption wavelength range is limited.

Further, JP-A-60-209583, JP-A-61-152685 and JP-A-64-62361 disclose synthetic examples in which 8 to 16 thioether groups are introduced into the phthalocyanine skeleton. . The method is
A phthalocyanine compound having 8 to 16 chlorine atoms and / or bromine atoms in a benzene nucleus of a phthalocyanine skeleton and an organic thiol compound are used as a KO in a quinoline solvent.
By heating in the presence of H, a phthalocyanine compound having 8 to 16 thioether groups in the benzene nucleus of the phthalocyanine skeleton is obtained. However, as with the above-mentioned ones, the yield is about 20 to 30%, and there is a problem in production efficiency. That is, the chloroether or bromine atom is poorly substituted with a thioether group, resulting in a low yield.For example, the chlorine atom is not substituted by the thioether group at all, or even if it is substituted, a part of the chlorine atom is a thioether group. The unreacted phthalocyanine compound which is merely replaced with is produced.

Since it is practically difficult to separate the unreacted phthalocyanine compound and the target phthalocyanine compound from each other, substantially only a mixture of phthalocyanine compounds having various compositions can be obtained. It's a reality. In fact, in JP-A-64-62361, it is described as a polythiol-substituted mixed condensation type phthalocyanine composition even after separation with a silica gel column, which shows that an unreacted type phthalocyanine compound remains. When some of the chloro atoms remain, their solubility is significantly reduced, and it is disadvantageous to dissolve them as a near-infrared absorbing dye or for other applications such as a visible absorption filter to form a thin film.

In JP-A-63-308073, monobromotetradecachlorophthalocyanine and 2-bromo
Aminothiophenol and an organic thiol mixture of 4-methylphenylthiol were heated in the presence of KOH in a DMF solvent to introduce thioether substituents to give the phthalocyanine compound in 42% yield. However, in this method, different organic thiol mixtures are simultaneously added and reacted, so that a phthalocyanine mixture having a kind of combination of thioether substituents can be obtained, and a single characteristic cannot be obtained, and the absorption wavelength is reduced. There is a problem that the use is limited when it is used as a cyan ink jet ink or a near infrared absorbing dye that needs to be controlled. Although it has solubility in a solvent, it is still at a low level and insufficient in terms of thin film formation or solubility in a resin.

JP-A-64-42283 and JP-A-3-42-
In each of the 62,878 publications, a near infrared absorbing dye in which an alkoxyl group or an alkylthio group is introduced into a phthalocyanine nucleus is proposed. However, most of them use a starting material having a substituent at the 3,6-position (α-position), which is poor in practicality, and there is a problem in practical use. It is still at a low level and insufficient in terms of thinning or solubility in resin. Further, in order to introduce a substituent to the 4,5-position (β-position), a phthalocyanine is derived from a chlorinated 4,5-position, so that the chlorine atom which is a factor that deteriorates the solubility due to its poor substitutability It also has the problem of remaining.

On the other hand, a phthalocyanine compound soluble in alcohols is disclosed in JP-A-63-295578. According to this, monobromotetradecachlorocopper phthalocyanine and 2-aminothiophenol and 4
-Substituted thiocopper such as hepta (4-methylphenylthio) -tetra (1-amino-2-thio-phenyl-1,2-ylene) -copper phthalocyanine obtained by reacting methylphenylthiol with an organic thiol mixture The phthalocyanine mixture is sulfonated with fuming sulfuric acid to obtain phthalocyanine having an average of 10 sulfonic acid groups, and then treated with a basic substance such as tetrabutylamine to convert it to a sulfonamide group, etc. A phthalocyanine compound having is obtained.

However, this method has the following problems. That is, some of the chloro atoms are likely to remain, and when some of the chloro atoms remain, their solubility is significantly reduced. The phthalocyanine compound is obtained as a mixture, and when it is used as a near-infrared absorbing dye, a single property cannot be obtained, so that its use is limited. The manufacturing process is very complicated, and the yield in each process is low. Since the sulfonation reaction is carried out in an aqueous system and the product is then purified by dialysis, there is a problem as an industrial production method.

In order to solve these drawbacks, the present inventors have selected an alkylthio group or an arylthio group to selectively replace the fluorine of octadecafluorophthalocyanine with a longer absorption wavelength and solubility in a solvent. Attempts were made to improve the results (Japanese Patent Application Nos. 1-209599, 2-125518, and 2-144292). Furthermore, for the purpose of further improving the solubility in a solvent and further increasing the absorption wavelength, a substituent was introduced at the 4 and 6-positions of the phthalocyanine skeleton, and the result was achieved (Japanese Patent Application No. 4- 23541 and JP-A-4-27913.
Specification). However, it was found that these phthalocyanine compounds are not always satisfactory in light resistance as described later.

On the other hand, many methods of using a phthalocyanine compound for an optical recording medium have been studied. The basic characteristics required when using a phthalocyanine compound in an optical recording medium include the following.

(B) The absorption wavelength is controlled according to the application. That is, it has an absorption peak required depending on the application. In addition, there are few absorption peaks due to association, which results in high absorbance and sharp absorption peaks.

(B) Practically, the dye can be formed into a thin film without using a complicated process such as vapor deposition or dispersion in a resin, that is, it can be applied by a simple and highly productive method such as spin coating, and Excellent solubility in a solvent that does not attack the substrate.

(C) The reflectance is high. (D) Good heat resistance and light resistance.

(E) High sensitivity.

(F) A compound which is economically advantageous in the production method and the like. That is, it can be manufactured simply and efficiently.

However, the phthalocyanine compounds proposed so far cannot satisfy all the above characteristics.

For example, JP-A-58-56892 proposes a method using a perfluorophthalocyanine compound. However, these compounds have poor solubility in organic solvents and cannot be controlled to a satisfactory absorption wavelength.

JP-A-61-219280, JP-A-63-
37991, JP-A-64-42283, JP-A-2-27
6677, JP-A-2-91360, JP-A-2-2657.
88, JP-A-3-215466, and JP-A-4-22639.
No. 0, etc. propose a phthalocyanine skeleton in which a substituent is introduced into the benzene ring via oxygen. However, these phthalocyanine compounds are
Depending on the type, number and position of the substituents on the dye, the light resistance is poor, the reflectance is low, it does not dissolve in a solvent such as polycarbonate that is commonly used directly on the substrate, or the absorption wavelength is controlled. There are some problems, such as difficulties.

As a solution to these drawbacks, a method in which four alkoxy groups are introduced at the α-position of phthalocyanine and a halogen compound or the like is partially introduced into the residue is disclosed in JP-A No. 5-1272. Is proposed. However, those having a substituent introduced at the α-position have problems in terms of economy, such as poor productivity from phthalonitrile as a raw material.

As a solution to the above problems, the present inventors have previously proposed a novel phthalocyanine compound having an oxy group introduced at the β-position of the benzene nucleus (Japanese Patent Application No. 4-
274125 and 4-262186).

[0029]

DISCLOSURE OF THE INVENTION The present invention is directed to 650 nm.
In the absorption wavelength region of ~ 800 nm, the absorption wavelength can be controlled according to the purpose, it has excellent properties such as excellent solubility in a solvent suitable for the application, such as an alcoholic solvent, and high light resistance. The present invention provides a novel phthalocyanine compound.

Further, when the present invention is used as an optical recording medium, particularly a write-once type optical recording medium for CD, the characteristics required for them are controllability of absorption wavelength, solubility in solvent used, thermal decomposition characteristics, It is intended to provide a novel phthalocyanine compound having excellent reflectance and light resistance.

The present invention also provides a method for efficiently producing the above novel phthalocyanine compound.

The present invention also provides a near infrared ray absorbing material comprising the above novel phthalocyanine compound.

The present invention also provides an optical recording medium containing the above novel phthalocyanine compound in the recording layer.

Further, the present invention provides a write-once type optical recording medium containing the above novel phthalocyanine compound in a recording layer.

[0035]

The present inventors have completed the present invention by finding that the novel fluorine-containing phthalocyanine compound represented by the following general formula (I) is a compound satisfying the above-mentioned object.

That is, one of the present invention is a fluorine-containing phthalocyanine compound represented by the following general formula (I).

General formula (I):

[0038]

[Chemical 9]

In the formula, X ¹ , X ² , X ³ and X ⁴ may be the same or different and each of the following substituents (1),
(2), (3), (4) or (5) and located at the β-position of the benzene nucleus; a, b, c and d may be the same or different and each represents 0 to 2 Is an integer and the sum of a, b, c and d is 1-3, preferably 2; F is a fluorine atom; and M is a metal, metal oxide, metal hydroxide or metal halide. is there.

Substituent (1):

[0041]

[Chemical 10]

Substituent (2):

[0043]

[Chemical 11]

The substituent _{(3): -O-C m} H n substituents _{(4): -O- (CH 2} CH 2 O) g B substituent _{(5) -O- (CH 2 CH} 2 CH 2 O ) _H G In the above formula, A, B and G are each an alkyl group having 1 to 8 carbon atoms; Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms. And at least one selected from a fluorine atom; D and E may be the same or different and each has 1 carbon atom.
Is an alkyl group of 4 to 4; g and h are each an integer of 1 to 5; p and r are each an integer of 0 to 2; m is an integer of 1 to 12; n is C _m H _n. Is the number of hydrogen atoms required to saturate the linear or branched alkyl group.

The β-position of the above-mentioned benzene nucleus means 2, 3, 6, 7, in the phthalocyanine nucleus represented by the following formula.
Meaning positions 10, 11, 14 and 15.

[0046]

[Chemical 12]

Another invention is 3,4,5,6-tetrafluorophthalonitrile, and 0.25 to 3 mol of a fluorinated phthalonitrile compound represented by the following general formula (II) with respect to 1 mol of the phthalonitrile. At least one phthalonitrile compound selected from the following, and the following general formula (III)
The method for producing a fluorine-containing phthalocyanine compound is characterized by reacting a metal oxide, a metal halide, or an organic acid metal salt represented by

General formula (II):

[0049]

[Chemical 13]

In the formula, X is the following substituents (1), (2),
(3), (4) or (5). Substituent (1)

[0051]

[Chemical 14]

Substituent (2)

[0053]

[Chemical 15]

Substituent (3) —O—C _m H _n Substituent (4) —O— (CH ₂ CH ₂ O) _g B Substituent (5) —O— (CH ₂ CH ₂ CH ₂ O) _h G In the above formula, A, B, G, Z, D, E, g, h, p, r,
m and n have the same meaning as described above.

Formula (III): Me _t Y _{z In the} formula, Me is a metal, Y is an oxygen, halogen or organic acid group, t is an integer of 1 to 3, and z is a metal Me and It is a value determined by the valence number of Y. Another invention has the above-mentioned fluorine-containing phthalocyanine compound,
A near-infrared absorbing material having absorption in a range of 650 nm to 800 nm.

Another invention is an optical recording medium containing the above-mentioned fluorine-containing phthalocyanine compound in a recording layer.

Another aspect of the present invention is a write-once type optical recording medium for a compact disc, comprising a transparent resin substrate, a recording layer containing a near-infrared absorber and a metal reflection layer, which are provided in this order. The write-once type optical recording medium is characterized in that the agent is a fluorine-containing phthalocyanine compound represented by the following general formula (IV).

General formula (IV):

[0059]

[Chemical 16]

Wherein X ¹ , X ² , X ³ , X ⁴ , a, b, c and d have the same meanings as above, and M is SnC.
_{l 2, SnBr 2, Sn (} OH) 2, GeCl 2, GeBr
₂ or Ge (OH) ₂ .

Substituent (1):

[0062]

[Chemical 17]

Substituent (4): —O— (CH ₂ CH ₂ O) _g B Substituent (5) —O— (CH ₂ CH ₂ CH ₂ O) _h G In the above formula, A, B, G, Z, g, h and p have the same meaning as described above.

The present invention will be described in detail below.

In the substituent (1), A has 1 carbon atom.
~ 8, preferably 1 to 5 alkyl groups, Z is a hydrogen atom, a C1 to C4 alkyl group, a carbon number 1 to 1
4 is at least one selected from an alkoxyl group and a fluorine atom, and p is an integer of 0 to 2.

Representative examples of the substituent (1) include phenoxy, o-methylphenoxy, p-methylphenoxy,
2,6-dimethylphenoxy, o-methoxyphenoxy, p-methoxyphenoxy, o-fluorophenoxy, p-fluorophenoxy, 2,3,5,6-tetrafluorophenoxy, o-methoxycarbonylphenoxy, p-methoxycarbonylphenoxy , M-methoxycarbonylphenoxy, o-ethoxycarbonylphenoxy, p-ethoxycarbonylphenoxy, m-ethoxycarbonylphenoxy, o-butoxycarbonylphenoxy, p-butoxycarbonylphenoxy, m-butoxycarbonylphenoxy, o-methyl-p-methoxy. Carbonylphenoxy, o-methoxy-p-methoxycarbonylphenoxy, o-fluoro-p-methoxycarbonylphenoxy, tetrafluoro-p-ethoxycarbonylphenoxy, o Ethoxycarbonylmethyl -p- methylphenoxy, o- butoxycarbonyl -p- methylphenoxy, o- butoxycarbonyl -p- fluorophenoxy, p- methyl -m- butoxycarbonyl phenoxy and the like.

In the substituent (2), Z is at least one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a fluorine atom, and D and E are They may be the same or different, each is an alkyl group having 1 to 4 carbon atoms, and r is an integer of 0 to 2.

Representative examples of the substituent (2) include dimethylaminophenoxy, diethylaminophenoxy, dibutylaminophenoxy and the like.

In the substituent (3), m is an integer of 1 to 12, preferably 1 to 8, and n is the number of hydrogen atoms necessary for saturating the linear or branched alkyl group C _m H _n. Is.

Representative examples of the substituent (3) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, linear or branched pentyloxy, linear or branched hexyloxy, and direct. Chain or branched heptyloxy, straight chain or branched octyloxy, straight chain or branched nonyloxy, straight chain or branched decyloxy, straight chain or branched hendecyloxy, straight chain or branched dodecyl Examples thereof include oxy and cyclohexyloxy.

In the substituents (4) and (5), B and G are each an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and g and h are each an integer of 1 to 5, preferably 1-3.

Representative examples of the substituents (4) and (5) are:
Methoxyethoxy, ethoxyethoxy, 3 ', 6'-oxaheptyloxy, 3', 6'-oxaoctyloxy, 3 ', 6', 9'-oxadecyloxy, 3 ',
6 ', 9'-oxahendecyloxy, 3', 6 ',
9 ', 12'-oxatridecyloxy, methoxybutoxy, ethoxybutoxy, 4', 8'-oxanonyloxy, 4 ', 8'-oxadecyloxy, 4', 8 ',
12'-oxatridecyloxy, 4 ', 8', 1
2 ', 16'-oxaheptadecyloxy etc. are mentioned.

In the general formula (I), typical examples of the central metal or metal compound of the phthalocyanine compound represented by M are Cu, Zn, Pb, Fe, Ni, Co,
Pd, AlCl, AlI, InCl, InI, GaC
1, GaI, TiCl ₂ , TiO, VCl ₂ , VO, Sn
Cl ₂ , SnBr ₂ , Sn (OH) ₂ , GeCl ₂ , GeB
r ₂ and Ge (OH) ₂ . Of these,
Ni, Co, Pd, AlCl, InCl, TiO, V
O, SnCl ₂ , Sn (OH) ₂ , GeCl ₂ and Ge
(OH) ₂ is particularly preferred.

In the general formula (IV), M '
Among Sn and Ge hydroxides and halides represented by, SnCl ₂ and GeCl ₂ are particularly preferable.

Typical examples of the fluorine-containing phthalocyanine compound represented by the above general formula (I) of the present invention are as follows.

(1) tetradecafluorodi (phenoxy) dichlorotin phthalocyanine (2) tetradecafluoro-bis (2,6-dimethoxyphenoxy) dichlorotin phthalocyanine (3) tetradecafluoro-bis (o-methoxycarbonylphenoxy) Dichlorotin phthalocyanine (4) Tetradecafluoro-bis (p-fluorophenoxy) dichlorotin phthalocyanine (5) Tetradecafluoro-bis (2,3,5,6-tetrafluorophenoxy) dichlorotin phthalocyanine (6) Tetradecafluor Rhobis (o-methoxycarbonylphenoxy) dichlorotin phthalocyanine (7) Tetradecafluoro-bis (p-ethoxycarbonylphenoxy) dichlorotin phthalocyanine (8) Tetradecafluorobis (m-butoxycal) Nirufenokishi) dichlorotin phthalocyanine (9) tetradecanoyl fluoro chromatography bis (o-methyl-p- methoxycarbonylphenoxy) dichlorotin phthalocyanine (10) tetradecanoyl fluoro chromatography bis (o-methoxy -p
-Methoxycarbonylphenoxy) dichlorotin phthalocyanine (11) tetradecafluoro-bis (o-fluoro-p
-Ethoxycarbonylphenoxy) dichlorotin phthalocyanine (12) tetradecafluoro-bis (o-butoxycarbonyl-p-ethylphenoxy) dichlorotin phthalocyanine (13) tetradecafluorodimethoxy-dichlorotin phthalocyanine (14) tetradecafluorodi ( tert-butoxy) -dichlorotin phthalocyanine (15) tetradecafluorodi (n-octyloxy) -dichlorotin phthalocyanine (16) tetradecafluorodiisopropoxydichlorotin phthalocyanine (17) tetradecafluoro-bis (methoxyethoxy) -dichlorotin Phthalocyanine (18) tetradecafluoro-bis (3 ', 6'-oxaheptyloxy) -dichlorotin phthalocyanine (19) tetradecafluoro-bis (3', 6 ' Oxa octyloxy) Jikuroro tin phthalocyanine (20) tetradecanoyl fluoro chromatography bis (3 ', 6', 9 '
-Oxadecyloxy) -dichlorotin phthalocyanine (21) tetradecafluoro-bis (3 ', 6', 9 '
-Oxadecyloxy) -dichlorotin phthalocyanine (22) tetradecafluoro-bis (3 ', 6',
9 ', 12'-oxatridecyloxy) -dichlorotin phthalocyanine (23) tetradecafluoro-bis (ethoxybutoxy) -dichlorotin phthalocyanine (24) tetradecafluoro-bis (4', 8'-oxanonyloxy) -dichloro Tin phthalocyanine (25) Tetradecafluoro-bis (4 ', 8'-oxadecyloxy) -dichlorotin phthalocyanine (26) Tetradecafluoro-bis (phenoxy) dibromotin phthalocyanine (27) Tetradecafluoro-bis (2,6 -Dimethylphenoxy) hydroxytin phthalocyanine (28) tetradecafluoro-bis (o-methoxycarbonylphenoxy) dichlorogermanium phthalocyanine (29) tetradecafluoro-bis (p-fluorophenoxy) hydroxygermanium phthalate Russianine (30) tetradecafluoro-bis (2,3,5,6-
Tetrafluorophenoxy) dibromogermanium phthalocyanine (31) Tetradecafluoro-bis (o-methoxycarbonylphenoxy) dichlorogermanium phthalocyanine (32) Tetradecafluoro-bis (p-ethoxycarbonylphenoxy) hydroxytin phthalocyanine (33) Tetradecafluoro Bis (dimethylaminophenoxy) dichlorotin phthalocyanine (34) tetradecafluoro-bis (m-butoxycarbonylphenoxy) dibromotin phthalocyanine (35) tetradecafluorodimethoxy-dichlorogermanium phthalocyanine (36) tetradecafluoro-bis (3 ' , 6'-Oxaheptyloxy) -dichlorogermanium phthalocyanine (37) tetradecafluoro-bis (3 ', 6'-oxac Yloxy)-hydroxy tin phthalocyanine (38) tetradecanoyl fluoro chromatography bis (3 ', 6', 9 '
-Oxadecyloxy) -dichlorogermanium phthalocyanine (39) tetradecafluoro-bis (m-dimethylaminophenoxy) copper phthalocyanine (40) tetradecafluoro-bis (m-diethylaminophenoxy) zinc phthalocyanine (41) tetradecafluoro-bis (P-Dibutylaminophenoxy) cobalt phthalocyanine (42) tetradecafluoro-bis (m-dimethylaminophenoxy) palladium phthalocyanine (43) tetradecafluoro-bis (3 ', 6', 9 '
-Oxadecyloxy) -dichlorogermanium phthalocyanine Among the above-mentioned fluorine-containing phthalocyanine compounds, particularly exemplified compounds (2), (3), (6), (7), (8),
(9), (10), (11), (12), (18),
(19), (20), (21), (22), (24),
(25), (28), (31), (36), (38) and (43) are preferred.

In the above-mentioned fluorine-containing phthalocyanine compound, the oxy substituent may be located at any β position of the benzene nucleus.

The fluorine-containing phthalocyanine compound represented by the above general formula (I) of the present invention is 650 nm to 800 nm.
It has absorption in the wavelength region of 1, is excellent in solubility in a solvent, has high reflectance, and is also excellent in heat resistance and light resistance. Further, the fluorine-containing phthalocyanine compound of the present invention has little association. Therefore, the absorption peak due to the associated molecule is small, and the absorbance of the fluorine-containing phthalocyanine compound is high, and the absorption peak is sharp.

A typical method for producing the fluorine-containing phthalocyanine compound represented by the above general formula (I) of the present invention will be described below.

According to this method, 3,4,5,6-tetrafluorophthalonitrile, and 0.25 to 3 mol of the fluorinated phthalonitrile represented by the general formula (II) per 1 mol of this phthalonitrile. At least one phthalonitrile compound selected from the compounds and the metal compound represented by the general formula (III) are reacted to obtain the target fluorine-containing phthalocyanine compound.

The above-mentioned general formula (II) which is one of the starting materials
The fluorinated phthalonitrile compound represented by
It can be easily obtained by subjecting 5,6-tetrafluorophthalonitrile and a compound represented by the formula XH (wherein X has the same meaning as described above) to a condensation reaction. This condensation reaction can be carried out in a solvent. As this solvent,
Inert solvents such as nitrobenzene, acetonitrile, benzonitrile, aprotic polar solvents such as pyridine, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, triethylamine, tri-n-butylamine, dimethylsulfone, sulfolane, etc. Can be used.

In the condensation reaction, a condensing agent generally used in this type of reaction can be used. Examples of the condensing agent include triethylamine and tri-n
-It is preferable to use organic bases such as butylamine and potassium fluoride. Further, a nucleophilic substitution reagent such as aniline, toydin, anisidine, n-butylamine, and n-octylamine can be used as the condensing agent.

Regarding the condensation reaction, Japanese Patent Application No. 63-6
5806, Japanese Patent Application No. 1-103554, Japanese Patent Application No. 1-103
555 and Japanese Patent Application No. 1-209599.

In the method for producing the fluorine-containing phthalocyanine compound represented by the above general formula (I) of the present invention, this reaction can be carried out in an organic solvent. The organic solvent may be any inert solvent that does not react with the starting material phthalonitrile, such as benzene,
Toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, ethylene glycol,
Inert solvent such as benzonitrile, or pyridine,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, triethylamine, tri-n-butylamine, dimethyl sulfone,
An aprotic polar solvent such as sulfolane can be used. Among these, chloronaphthalene, trichlorobenzene, benzonitrile and N-methyl-2-
Pyrrolidinone is particularly preferably used.

Specifically, the total amount of 3,4,5,6-tetrafluorophthalonitrile and the fluorine-containing phthalonitrile compound represented by the general formula (II) is 2 to 30 relative to 100 parts by weight of the organic solvent. It is preferable to charge in the range of parts by weight. The ratio of the fluorinated phthalonitrile compound represented by the general formula (II) to 1 mol of 3,4,5,6-tetrafluorophthalonitrile is 0.25 to 3 mol, and particularly 0.8 to 1.2 mol. Is preferred. Three
When the ratio of 4,5,6-tetrafluorophthalonitrile is increased, a large amount of hexadecafluorophthalocyanine is produced, which makes the separation from the intended product complicated, which is not preferable. On the other hand, when the ratio of the fluorine-containing phthalonitrile compound represented by the general formula (II) is increased, a large number of substituents are introduced, so that good characteristics cannot be obtained for use in a near infrared absorbing material such as an optical recording medium. Not preferable.

According to the method of the present invention, 3,4,5,6-tetrafluorophthalonitrile and the fluorinated phthalonitrile compound (3,4,5,6) represented by the above general formula (II) are used.
-0.25 to 3 times the molar amount of tetrafluorophthalonitrile) and a desired amount of the metal compound represented by the general formula (III), the substituent (1),
(2), (3), (4) or (5) is β of the benzene nucleus
An average of two fluorine-containing phthalocyanine compounds introduced at each position is obtained. At this time, a fluorine-containing phthalocyanine compound in which one or three of the above-mentioned substituents are introduced may be produced, but these may be appropriately separated. Usually, since the production ratio of the fluorine-containing phthalocyanine compound having one or three substituents introduced therein is low, even a mixture with the fluorine-containing phthalocyanine having two substituents introduced therein is a near-infrared absorbing material. If there is no particular adverse effect on the properties when used as, especially its unity, it may be used as a mixture as it is. The amount of the metal compound represented by the general formula (III) used is not particularly limited, and usually,
The metal compound is added in an amount of 0.25 to 0..5 with respect to a total of 1 mol of 3,4,5,6-tetrafluorophthalonitrile and the fluorine-containing phthalonitrile compound represented by the general formula (II).
It is desirable to use it in a ratio of 40 mol.

The reaction temperature is preferably in the range of 100 to 250 ° C, particularly preferably in the range of 120 to 200 ° C. The reaction is usually performed at normal pressure.

In the above general formula (III), Me is a metal such as copper, zinc, lead, cobalt, nickel, iron, aluminum, indium, gallium, titanium, vanadium, tin and germanium, and Y is an oxygen atom or halogen. Atoms (preferably chlorine and iodine) or organic acid salts (preferably oxalate and acetate).

Typical examples of the metal compound represented by the general formula (III) include cuprous chloride, cupric chloride, cuprous iodide, zinc chloride, zinc iodide, lead chloride, lead acetate, Cobalt chloride, cobalt acetate, nickel chloride, nickel acetate, ferrous chloride, ferric chloride, aluminum chloride, indium chloride, gallium chloride, titanium chloride, vanadium trichloride, vanadium oxytrichloride, vanadium pentoxide, ferrous chloride Examples thereof include tin, stannic chloride, tin oxalate and germanium chloride. Of these, cuprous chloride, zinc iodide, cobalt chloride, nickel chloride, ferric chloride, indium chloride, vanadium trichloride, stannous chloride and germanium chloride are particularly suitable.

The fluorine-containing phthalocyanine compound represented by the general formula (I) of the present invention has 1 to 3 (preferably 2) selected from the substituents (1) to (5) at the β-position of the benzene nucleus. ) Has a fluorine atom introduced into the substituent and the residue, has absorption in the wavelength region of 650 nm to 800 nm, and has excellent properties such as solubility in a solvent, reflectance, thermal decomposition, and light resistance. There is. Therefore, the fluorinated phthalocyanine compound of the present invention is used as a near-infrared absorbing material having absorption at 650 nm to 800 nm. In particular,
CD or CD-R, which requires the above characteristics
It exhibits an excellent effect when used as a write-once type optical recording medium having compatibility and commonality with OM players, or an optical recording medium such as an optical disc, a laser disc, an optical card and the like.

Specifically, a write-once type optical recording medium compatible with a compact disk, which is formed by providing a recording layer containing a near-infrared absorbing agent and a metal reflective layer on a transparent resin substrate in this order, for example, music such as audio. CD for playback, PHOTO-CD for storing photos or CD for computer
-Used as a near-infrared absorber of a write-once type optical recording medium which is compatible and compatible with ROM players.

As the disk substrate used for manufacturing the write-once type optical recording medium, a transparent resin substrate through which light for recording or reading a signal is transmitted is used. It is desirable that the resin substrate has a light transmittance of 85% or more and a small optical anisotropy. For example, a resin substrate made of acrylic resin, polycarbonate resin, polyester resin, polyamide resin, vinyl chloride resin, polystyrene resin, epoxy resin, or the like is used. Of these, polycarbonate resin is preferable from the viewpoints of optical properties, ease of molding, mechanical strength, and the like.

A recording layer containing a near-infrared absorber is first formed on the transparent resin substrate, and a metal reflection film layer is formed on the recording layer to obtain a write-once type optical recording medium. Examples of the metal used as the reflective layer include Al, Ag, Au, Cu and Pt. This reflective layer is usually formed by a method such as vacuum deposition or sputtering.

In the optical recording medium or the write-once type optical recording medium of the present invention, in order to form a recording layer containing a near-infrared absorbing material or a near-infrared absorbing agent on a substrate, it is usually preferable to use a coating method. . As a coating method, a spin coating method, a dipping method, a roll coating method or the like is used. The spin coating method is particularly preferable. As the organic solvent used at that time, one that does not attack the resin substrate is used. For example, aliphatic, alicyclic hydrocarbon solvents such as hexane, octane and cyclohexane, and alcohol solvents such as methyl alcohol, isopropyl alcohol, allyl alcohol, methyl cellosolve and ethyl cellosolve are preferably used. The fluorine-containing phthalocyanine compound represented by the above general formula (I) of the present invention is particularly well soluble in an alcohol solvent, and therefore it is preferable to use these solvents.

In the case of the write-once type optical recording medium, the reflectance for the reading laser light through the resin substrate is required to be 60% or more from the viewpoint of compatibility with the player. The ratio can be adjusted by optimizing the film thickness of the recording layer according to the type of the fluorinated phthalocyanine compound of the present invention used as a near infrared absorber. Generally, the thickness of the recording layer is preferably 50 nm to 300 nm.

[0096]

INDUSTRIAL APPLICABILITY The fluorine-containing phthalocyanine compound represented by the general formula (I) of the present invention has 1 to 3 specific oxy substituents at the β-position of the benzene nucleus of the phthalocyanine skeleton and a fluorine atom at the residue. So 650nm ~ 800
It has absorption in the wavelength region of nm and has excellent properties such as solubility in a solvent.

From such characteristics, the fluorine-containing phthalocyanine compound represented by the general formula (I) of the present invention is useful as a near infrared absorbing material.

Particularly, the fluorine-containing phthalocyanine compound represented by the general formula (IV) of the present invention has the following characteristics.

(A) It has absorption in the wavelength region of 650 nm to 800 nm.

(B) It has excellent solubility in a solvent, particularly an alcohol solvent. Therefore, it can be applied by a simple and highly productive method such as spin coating.

(C) It has excellent heat resistance and light resistance.

(D) Little molecular association. Therefore, there are few absorption peaks due to associated molecules, and the absorbance in the maximum absorption wavelength region is high.

From such characteristics, the fluorine-containing phthalocyanine compound represented by the general formula (IV) of the present invention is
It is extremely useful as a near-infrared absorbing material for optical recording media such as write-once type optical recording media.

The fluorine-containing phthalocyanine compound represented by the general formula (I) of the present invention includes 3,4,5,6-tetrafluorophthalonitrile, the fluorine-containing phthalonitrile represented by the general formula (II) and the general formula Formula (III)
Since it can be easily obtained by reacting the metal compound represented by the above, according to the method of the present invention, the target fluorine-containing phthalocyanine compound can be easily obtained in high yield. Furthermore, since the method consists of a single reaction step,
It is possible to obtain a highly pure fluorine-containing phthalocyanine compound without the need for operations such as separation and purification of intermediate products, which are required in the case of a method comprising a plurality of reaction steps.

[0105]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 Tetradecafluoro-bis (p-ethoxycarbonylphenyl)
Enoxy) dichlorotin phthalocyanine (Exemplified compound
Synthesis of (7)) In a 100 ml four-necked flask, 6.0 g (30 mmol) of 3,4,5,6-tetrafluorophthalonitoyl (hereinafter abbreviated as "TFPN"), as a substituted phthalonitrile. 4- (p-ethoxycarbonylphenoxy)-
3,5,6-Trifluorophthalonitrile 10.4 g
(30 mmol), 3.2 g (8.3 mmol) of anhydrous stannous chloride as a metal compound and benzonitrile 60
ml was charged and the reaction was carried out at 175 ° C. for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of isopropyl ether to obtain 17.2 g of a target green cake (yield (TFPN + substituted phthalonitrile total standard, the same applies hereinafter): 91.9 mol%).

The analysis results of this cake were as follows.

Visible absorption spectrum Maximum absorption wavelength in methyl cellosolve 712.5 nm
(Ε = 9.36 × 10 ⁴ ) Thin film
Solubility in 725.0 nm methyl cellosolve 14% by weight Elemental analysis (%) H C N F Theoretical value 1.41 46.83 9.86 20.74 Analytical value 1.69 48.02 9.36 19.57 Example 2-3 Synthesis of Exemplified Compound (7) Exemplified Compound (7) was produced in the same manner as in Example 1 except that the charged amounts of TFPN and substituted phthalonitrile were changed as shown in Table 1. The yield is shown in Table 1.

Example 4 Synthesis of Exemplified Compound (2) Exemplified Compound (2) was produced in the same manner as in Example 1 except that the phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile. The yield is shown in Table 1.

[0110]

[Chemical 18]

Example 5 Synthesis of Exemplified Compound (4) Exemplified Compound (4) was produced in the same manner as in Example 1 except that the phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile. The yield is shown in Table 1.

[0112]

[Chemical 19]

Example 6 Synthesis of Exemplified Compound (9) Exemplified Compound (9) was produced in the same manner as in Example 1 except that the phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile. The yield is shown in Table 1.

[0114]

[Chemical 20]

Example 7 Synthesis of Exemplified Compound (15) Exemplified Compound (15) was produced in the same manner as in Example 1 except that the phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile. The yield is shown in Table 1.

[0116]

[Chemical 21]

Example 8 Synthesis of Exemplified Compound (21) Exemplified Compound (21) was produced in the same manner as in Example 1 except that the phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile. The yield is shown in Table 1.

[0118]

[Chemical formula 22]

Example 9 Synthesis of Exemplified Compound (24) In Example 1, except that a phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile and tin oxalate was used as the metal compound instead of anhydrous stannous chloride. Example 1
Exemplified compound (24) was produced in the same manner as. The yield is shown in Table 1.

[0120]

[Chemical formula 23]

Example 10 Synthesis of Exemplified Compound (28) Exemplified Compound (28) was produced in the same manner as in Example 1 except that the phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile. The yield is shown in Table 1.

[0122]

[Chemical formula 24]

Example 11 Synthesis of Exemplified Compound (38) In Example 1, except that a phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile and germanium tetrachloride was used as the metal compound instead of anhydrous stannous chloride. Exemplified compound (38) was synthesized in the same manner as in Example 1.
The yield is shown in Table 1.

[0124]

[Chemical 25]

Example 12 Synthesis of Exemplified Compound (40) In Example 1, except that a phthalonitrile compound represented by the following formula was used as the substituted phthalonitrile and zinc iodide was used as the metal compound instead of anhydrous stannous chloride. Example 1
Exemplified compound (40) was produced in the same manner as. The yield is shown in Table 1.

[0126]

[Chemical formula 26]

[0127]

[Table 1]

Example 13 With respect to the fluorine-containing phthalocyanine compound obtained in Examples 1 to 12, its absorption wavelength, solubility, light resistance and association property were measured. The results are shown in Table 2.

Absorption wavelength The maximum absorption wavelength and the molar extinction coefficient were measured as a methyl cellosolve solution.

Solubility The solubility in methyl cellosolve at 25 ° C. was measured,
The following three-stage evaluation was performed.

◯: Solubility of 10% or more Δ: Solubility of 5 to 10% X: Solubility of less than 5% A light-resistant fluorine-containing phthalocyanine compound was added to methyl cellosolve 20.
g and dissolved on a glass substrate by spin coating to form a thin film. This sample was set in a xenon light resistance tester (irradiation light amount: 100,000 Lux), and the absorbance at the maximum absorption wavelength over time was measured. And 100
The absorbance after the lapse of time was measured, the residual rate of the absorbance was determined according to the following formula, and the evaluation was performed in three stages.

Residual rate of absorbance (%) = (initial absorbance-1
Absorbance after 00 hours) / (initial absorbance) (× 10
0) ○: Residual rate of absorbance is 80% or more Δ: Residual rate of absorbance is 30 to 80% ×: Residual rate of absorbance is less than 30% The associative fluorine-containing phthalocyanine compound is dissolved in methyl cellosolve at a concentration of 10% by weight and spin A thin film was formed by coating on glass with a coater. The absorption spectrum of this thin film was measured, and from the absorption absorbance (A) derived from the fluorinated phthalocyanine compound on the long wavelength side and the absorption absorbance (B) derived from the aggregate on the short wavelength side, the ratio was calculated by the following formula. Was calculated and evaluated in the following three stages.

Association ratio (%) = (B) / (A) (× 100) ◯: Association ratio 10% or less Δ: Association ratio 10 to 20% ×: Association ratio 20% or more

[0134]

[Table 2]

Example 14 Exemplified compound obtained in Example 1 on a polycarbonate resin substrate having a depth of 80 nm, a spiral guide groove having a pitch of 1.6 μm, a thickness of 1.2 mm, an outer diameter of 120 mm and an inner diameter of 15 mm. A solution prepared by dissolving (7) in methoxy cellosolve at a concentration of 10% by weight was applied using a spin coater,
A film having a film thickness of 145 nm was formed. Next, gold (Au) was vacuum-deposited on the coating film thus obtained to obtain a film thickness of 7
The film was formed at 0 nm. Further, a protective coating film made of an ultraviolet curable resin was provided on this to prepare an optical recording medium.

About this optical recording medium, 770 nm-8
When the reflectance in the wavelength range of 00 nm was measured, it was 75
%, And stable optical characteristics were obtained.

A reflectance semiconductor laser is incident from the resin substrate side of the optical recording medium,
The reflectance was obtained by measuring the energy of incident light and the energy of reflected light.

Further, regarding the above optical recording medium, a wavelength of 7
Using an 80 nm semiconductor laser, output 6.5 mW,
When an EMF signal with a linear velocity of 1.4 m / s was recorded, recording was possible. When the obtained signal was analyzed, it was at a level that could be reproduced by a commercially available CD player.

Examples 15 to 19 In the same manner as in Example 14 except that the exemplified compounds (2), (9), (21) and (26) were used in place of the exemplified compound (7). An optical recording medium was created.

The reflectance of each of these optical recording media was measured in the same manner as in Example 14. The reflectance was 75% or more, and stable optical characteristics were obtained.

Further, when an EMF signal was recorded on these optical recording media in the same manner as in Example 14, recording was possible. When the obtained signal was analyzed, it was at a level that could be reproduced by a commercially available CD player.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaji Ito 12-25 Kannondai, Tsukuba-shi, Ibaraki 12 Incorporated company Nippon Shokubai Tsukuba Research Laboratories

Claims (5)

[Claims] 1. A fluorine-containing phthalocyanine compound represented by the following general formula (I). General formula (I): In the formula, X ¹ , X ² , X ³ and X ⁴ may be the same or different, and each of the following substituents (1), (2), (3),
(4) or (5), which is located at the β-position of the benzene nucleus; a, b, c and d, which may be the same or different, are each an integer of 0 to 2 and a, b , C and d
Is 1 to 3; F is a fluorine atom; and M is a metal, a metal oxide, a metal hydroxide or a metal halide. Substituent (1): Substituent (2): Substituents _{(3): - O-C} m H n substituents (4): - O- (CH 2 CH 2 O) g B substituent _{(5) -O- (CH 2 CH} 2 CH 2 O) h G In the above formula, A, B and G are each an alkyl group having 1 to 8 carbon atoms; Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and a fluorine atom. And D and E may be the same or different and each has 1 carbon atom.
Is an alkyl group of 4 to 4; g and h are each an integer of 1 to 5; p and r are each an integer of 0 to 2; m is an integer of 1 to 12; n is C _m H _n. Is the number of hydrogen atoms required to saturate the linear or branched alkyl group. 2. 3,4,5,6-Tetrafluorophthalonitrile, 0.25 to 1 mol of the phthalonitrile.
3 mol of at least one phthalonitrile compound selected from the fluorine-containing phthalonitrile compounds represented by the following general formula (II), and a metal oxide, metal halide or organic acid metal salt represented by the following general formula (III). The method for producing a fluorine-containing phthalocyanine compound according to claim 1, wherein the reaction is carried out. General formula (II): In the formula, X is the following substituents (1), (2), (3), (4)
Or (5). Substituent (1) embedded image Substituent (2) embedded image Substituents _{(3) -O-C m H} n substituents _{(4) -O- (CH 2 CH} 2 O) g B substituent _{(5) -O- (CH 2 CH} 2 CH 2 O) h G above formula Wherein A, B and G are each an alkyl group having 1 to 8 carbon atoms; Z is selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms and a fluorine atom. D and E may be the same or different and each has 1 carbon atom.
Is an alkyl group of 4 to 4; g and h are each an integer of 1 to 5; p and r are each an integer of 0 to 2; m is an integer of 1 to 12; n is C _m H _n. Is the number of hydrogen atoms required to saturate the linear or branched alkyl group. Formula (III): Me _t Y _{z In the} formula, Me is a metal, Y is an oxygen atom, a halogen atom or an organic acid group; t is an integer of 1 to 3; and z is Me or Y. It is a value determined by the valence number. 3. A near-infrared absorbing material comprising the fluorine-containing phthalocyanine compound according to claim 1 and absorbing in the range of 650 nm to 800 nm. 4. An optical recording medium containing the fluorine-containing phthalocyanine compound according to claim 1 in a recording layer. 5. A write-once type optical recording medium for a compact disc, comprising a transparent resin substrate, on which a recording layer containing a near-infrared absorbing agent and a metal reflecting layer are provided in this order, wherein the near-infrared absorbing agent is: A write-once type optical recording medium, which is a fluorine-containing phthalocyanine compound represented by the general formula (IV). General formula (IV): In the formula, X ¹ , X ² , X ³ and X ⁴ may be the same or different and each is represented by the following general formula (1), (4) or (5).
At the β-position of the benzene nucleus; a, b, c and d, which may be the same or different, are each an integer of 0 to 2, and the sum of a, b, c and d is 1 to 3; F is a fluorine atom; and M ′ is SnCl ₂ ,
_{SnBr 2, Sn (OH) 2} , GeCl 2, is a GeBr ₂ or Ge (OH) _2. Substituent (1): Substituents _{(4): -O- (CH 2} CH 2 O) g B substituent _{(5) -O- (CH 2 CH} 2 CH 2 O) h G above formula, A, B and G are each a carbon atom An alkyl group having 1 to 8; Z is at least one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a fluorine atom; and g and h are each Is an integer from 1 to 5; and p is an integer from 0 to 2.