JP2005298490A - Phthalocyanine compound, organic dye using the same, and optical recording medium - Google Patents

Abstract

［式中、Ｘ１〜Ｘ４は、置換基を有してもよいアルキル基などを表す。Ｙｌ〜Ｙ４は、ハ
ロゲン原子などを表す。Ｒ１、Ｒ２は、アルキル基などを表す。Ａｒは芳香環などを表す。
ｍ１〜４，ｎ１〜４は、０〜４の整数を表す。］

An object of the present invention is to provide an optical recording medium capable of supporting ultra-high-speed recording such as 48 times and 52 times the speed of an optical recording medium, and a phthalocyanine compound and an organic dye capable of realizing this, and is suitable for high-speed recording. An phthalocyanine compound represented by the following general formula (1) is provided.
General formula (1)
[Chemical 1]

[In formula, X1-X4 represents the alkyl group etc. which may have a substituent. Yl to Y4 represent a halogen atom or the like. R1 and R2 represent an alkyl group or the like. Ar represents an aromatic ring or the like.
m1-4 and n1-4 represent the integer of 0-4. ]

Description

  The present invention relates to a novel phthalocyanine compound, an organic dye containing the same, and an optical recording medium. In particular, a phthalocyanine compound that exhibits good high-speed recording characteristics when used as an organic dye constituting a recording layer of an optical recording medium capable of recording and reproducing information by laser light, an organic dye using the same, and an optical recording medium About.

  Currently, a CD-R conforming to a CD format or a CD-ROM format has been put to practical use as a write-once type optical recording medium. This CD-R has a structure in which a recording layer made of an organic dye or the like, a reflective layer, and a protective layer are sequentially laminated on a substrate, and heat mode recording is performed by a semiconductor laser having a wavelength of 780 nm. In other words, the laser light applied to the recording layer is converted into thermal energy by absorption of the organic dye, and the generated heat causes alteration of the organic dye or the like, or deformation of the substrate, which changes the optical characteristics and is not irradiated. Contrast with the part occurs. As such a recording layer, one using a phthalocyanine dye as an organic dye material for the recording layer has been proposed, and some compounds have been put into practical use (see Patent Documents 1 to 3 below).

In recent years, the recording speed has been rapidly increased, and a recording drive capable of recording at 48 times speed, 52 times speed or higher speed is becoming popular in the current market. Along with this, high-speed recording suitability is also required for CD-R media, and it is necessary to cope with speed recording from constant speed recording to 48 times speed, 52 times speed or more on the same medium.
During high-speed recording, the irradiation time becomes shorter as the recording speed increases, but since the output of the semiconductor laser is limited, it is expected that the irradiation dose will decrease and the sensitivity will be insufficient to form an appropriate recording. In order to increase the sensitivity, it is conceivable to increase the thermal energy generated by increasing the light absorption of the organic dye, but when reproducing the optical record, a weak laser is irradiated to read the information by changing the reflectivity. In the handling method, there is a possibility that information cannot be read if reproduction is repeated. In addition, when left in direct sunlight, the recording surface changes in quality on the entire surface of the CD-R medium, and similarly, there is a possibility that recorded information cannot be read. Therefore, it is required to respond efficiently to the laser during recording, but not to be altered during reproduction or environmental light.

  In addition, in response to the trend of price reduction of CD-R media, a reduction in manufacturing cost is also an important factor. In order to increase the efficiency of producing a CD-R medium using the same apparatus, it is necessary to shorten the time (cycle time) required for production per sheet. High is also important. In other words, if the solubility of the dye used is poor, the dye concentration of the coating solution must be set low, and the cycle time required to obtain a sufficient dye film thickness capable of suitable recording becomes longer, and the disk Productivity decreases and manufacturing costs increase. So far, the present inventors have proposed an optical recording medium using a phthalocyanine compound having an axial substituent on the central metal in order to obtain high solubility and suitability for coating, improving solubility and improving productivity. (See Patent Documents 1, 2, and 4 below).

In the phthalocyanine compound, an axial substituent that can improve the durability of the optical recording medium includes a siloxy group. An optical recording medium using a phthalocyanine compound having a siloxy group as an axial substituent is disclosed in Patent Documents 5 and 6 below. Has been proposed in
Japanese Examined Patent Publication No. 4-53713 JP-A-4-214388 Japanese Patent Laid-Open No. 5-1272 WO97 / 23354 pamphlet JP-A 61-177288 JP-A-1-228894

  The reason why the durability is improved in the case of a phthalocyanine compound in which the axial substituent is a siloxy group may be that the bond between the central aluminum of the phthalocyanine and the siloxane is stable, but this stability also causes a decrease in sensitivity. It is expected that. In fact, an optical recording medium using a conventional phthalocyanine compound having a siloxy group is insufficient in sensitivity even for high-speed recording of about 40 times speed.

  An object of the present invention is to provide an optical recording medium that can cope with ultra-high-speed recording such as 48 times and 52 times the speed of an optical recording medium, and a phthalocyanine compound and an organic dye that can realize this, and can be suitably used for high-speed recording. It is to realize an optical recording medium.

The inventors of the present application have studied various siloxyaluminum phthalocyanine compounds, and found that the sensitivity can be improved only when a dialkylarylsiloxyaluminum phthalocyanine compound is used without deteriorating the reproduction deterioration of the optical recording medium.
According to one embodiment of the present invention, a phthalocyanine compound has a structure represented by the following general formula (1).

[Wherein, X1 to X4 may be the same or different, and each may have an alkyl group that may have a substituent, an aryl group that may have a substituent, or an cycloalkyl that may have a substituent. Group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a substituent Represents an organic group selected from the group consisting of an alkylthio group which may have an arylthio group and an arylthio group which may have a substituent. Yl to Y4 may be the same or different and each represents an organic group selected from the group consisting of a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, and a sulfonamide group. R1 and R2 may be the same or different and each represents an alkyl group which may have a substituent. Ar represents an aromatic ring which may have a substituent. m1, m2, m3, m4, n1, n2, n3, and n4 each represents an integer of 0 to 4, and may be the same or different. m1 + n1, m2 + n2, m3 + n3, m4 + n4 are It may be the same or different. ]

The phthalocyanine compound in which at least one of the organic groups X1 to X4 is an alkyl group which may have a substituent or an alkoxy group which may have a substituent can provide a particularly suitable optical recording medium. Becomes an organic dye.

  According to one aspect of the present invention, the organic dye of the present invention contains at least one phthalocyanine compound.

  Furthermore, according to one aspect of the present invention, the optical recording medium of the present invention has an optical recording layer containing at least one phthalocyanine compound on a substrate.

  According to the present invention, it is possible to provide a siloxyaluminum phthalocyanine compound capable of realizing an optical recording medium that can cope with ultrahigh-speed recording, which can be used as an organic dye. Further, by using this compound, it is possible to provide an optical recording medium which is excellent in reproduction deterioration and can be recorded at high speed.

  The present inventors examined phthalocyanine having a siloxy group as an axial group. When the siloxy group is a triarylsiloxy group, the recording can be handled at about 40 times speed, and sensitivity can be increased, and jitter is increased. Has been found in Japanese Patent Application (Japanese Patent Application No. 2004-043890). However, even with an optical recording medium containing this type of phthalocyanine compound, 48-speed recording and 52-times speed recording, which are higher speeds, are difficult to handle due to insufficient sensitivity.

  In the present application, an aluminum phthalocyanine compound having a dialkylarylsiloxy group as an axial group is proposed as an organic dye compound for a recording layer capable of realizing an optical recording medium compatible with 48 × speed recording and 52 × speed recording. Within the scope of our investigation, aluminum phthalocyanine having a dialkylarylsiloxy group as an axial group has not been known.

  In the present invention, the organic dye constituting the recording layer of the optical recording medium contains at least one phthalocyanine compound represented by the general formula (1).

Hereinafter, the structure, substituents and the like represented by the general formula (1) will be described in detail.
The phthalocyanine compound (1) used in the optical recording medium of the present invention has a siloxy group as an axial group, and the groups R1 and R2 are directly bonded to silicon of the siloxy group. The benzene ring of the phthalocyanine skeleton may be substituted with organic groups X1 to X4 and Y1 to Y4. The numbers n1 to n4 of the organic groups X1 to X4 and the numbers m1 to m4 of the organic groups Y1 to Y4 are each 0 to 4, which may be the same or different. m1 + n1, m2 + n2, m3 + n3, m4 + n4 are each 0-4. Accordingly, hydrogen is bonded to the benzene ring of the phthalocyanine skeleton unless it is substituted with organic groups X1 to X4 and Y1 to Y4.

  In the phthalocyanine compound (1), the organic groups R1 and R2 directly bonded to the silicon of the siloxy group each represent an alkyl group that may have a substituent, and may be the same or different. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, ptyl group, isoptyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group, 2-ethylhexyl. Examples of the substituent in the case where R1 or R2 is an alkyl group having a substituent include alkoxy groups such as chlorine, fluorine and bromine, alkoxy groups such as methoxy group, phenyl, etc. Group, aromatic group such as tolyl group, nitro group and the like. There may be a plurality of substituents, or a substituent in which a plurality of types of groups in the above examples are connected in series. Examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and a 2-butoxyethyl group. 2-nitropropyl group, benzyl group, 4-methylpentyl group, 4-tert-butylpentyl group, 4-methoxypentyl group, 4-nitrobenzyl group, 2,4-dichloropentyl group, and the like. In addition, it is preferable that carbon number of organic group R1 R2 is 1-12 from a viewpoint of taking many state changes per dye molecule | numerator and making a sensitivity high.

  The organic group Ar directly bonded to the silicon of the siloxy group represents an aromatic ring that may have a substituent. The aromatic ring includes a phenyl group, a naphthyl group, an anthranyl group, and the like. When Ar is an aromatic ring having a substituent, the substituent includes a halogen atom, an alkyl group, an alkoxy group, an amino group, a nitro group, and the like. is there. There may be a plurality of substituents, or a substituent in which a plurality of the above-mentioned substituent examples are bonded in series. Examples of the aromatic ring having a substituent include p-tolyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylamino group. Examples include phenyl group, 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

In the general formula (1), the organic groups (X1 to X4) represented by X may be the same or different. Specific examples thereof include an alkyl group which may have a substituent and a substituent. An aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryl which may have a substituent Examples thereof include an oxy group, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent. When the organic groups X1 to X4 have a substituent, the substituents may be the same or different. Specific examples thereof include halogen groups such as fluorine, chlorine and bromine, amino groups, hydroxy groups, nitro groups and the like. In addition to characteristic groups, alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and the like can be given. Moreover, there may be a plurality of substituents, and a substituent in which a plurality of types of groups in the above examples are bonded in series may be used.

  As long as the organic group X is not a chemically unstable group or a highly reactive group, the difference in the organic group X does not significantly affect the film formability of the phthalocyanine compound of the formula (1) and the characteristics as a recording film. When the carbon number of X is small, the solubility of the phthalocyanine compound is low, and when the carbon number is large, the extinction coefficient per mass of the compound decreases and the amount necessary for the recording film increases, so that the organic compound having 2 to 12 carbon atoms. A group is preferred. Further, the substitution positions of X1 to X4 are the 1-position and / or 4-position, 8-position and / or 11-position, 15-position and / or 18-position, 22-position and / or 25-position phthalocyanine compound which is 2-position And / or 9-position and / or 10-position, 16-position and / or 17-position, 23-position and / or 24-position, since the solubility becomes higher.

  Examples of the “alkyl group” of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, There are linear or branched alkyl groups such as n-octyl group, stearyl group and 2-ethylhexyl group, and examples of the “alkyl group having a substituent” include trichloromethyl group, trifluoromethyl group, 2,2,2 -Trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pendyl group, 4- Examples include methylpentyl group, 4-tert-butylbenzyl group, 4-methoxypentyl group, 4-nitrobenzyl group, and 2,4-dichlorobenzyl group.

  Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthranyl group, and the “aryl group having a substituent” includes a p-methylphenyl group and a p-bromo group. Phenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like.

  Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like, and the “cycloalkyl group having a substituent” includes 2,5- Examples include dimethylcyclopentyl group and 4-tert-butylcyclohexyl group.

  Examples of the “heterocyclic group” of the heterocyclic group which may have a substituent include a pyridinyl group, a birazinyl group, a piperidinyl group, a biranyl group, a morpholinyl group, an acridinyl group, and the like, and a “heterocyclic group having a substituent” As such, there are a 3-methylpyridinyl group, an N-methylpiperidinyl group, an n-methylpyrrolinyl group, and the like.

  As the “alkoxy group” of the alkoxy group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-butyloxy group, a neopentyloxy group , 2,3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc. Examples of the “alkoxy group” include trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. A.

  Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthranyloxy group, and the like, and the “aryloxy group having a substituent” includes a p-methylphenoxy group. P-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, and the like.

  Examples of the alkylthio group which may have a substituent and the arylthio group which may have a substituent include those in which the oxygen atom of the alkoxy group or aryloxy group is replaced with a sulfur atom.

In order to improve the solubility of the phthalocyanine compound in a solvent, at least one of the organic groups X1 to X4 is preferably an organic group or each of the four organic groups is an alkyl group or an alkoxy group, or X1 It is preferable that at least one of -X4 is a group substituted with an alkyl group or an alkoxy group. Furthermore, preferably, at least one of X1 to X4 is a branched alkoxy group, more preferably a branched alkoxy group having 2 to 8 carbon atoms. More preferably, it is a saturated alkyloxy group consisting of a branched carbon atom having 2 to 8 carbon atoms and a hydrogen atom. Although the factor is not certain, the degree of modulation increases when an optical recording medium is used.

Specific examples of the organic group (Y1 to Y4) represented by Y include a halogen atom, a nitro group, and an optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —). And sulfonamide group (H ₂ NSO ₂ —). Preferred Y is a halogen atom and a sulfonamide group. A phthalocyanine compound in which m1 to m4 are 0 (that is, there is no organic group Y) can also be suitably used.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the “substituent” of the phthalimidomethyl group which may have a substituent and the sulfonamide group which may have a substituent include the above alkyl groups, aryl groups, and nitro groups.

The organic groups X and Y are elements that affect the solubility of the phthalocyanine compound in the solvent. When the organic group X or Y is included, the film forming property of the optical recording layer containing the phthalocyanine compound is improved.

  In the present invention, typical examples of the organic dye composition represented by the general formula (1) include phthalocyanine compounds (a) to (e) shown below, but are not limited thereto. .

Phthalocyanine compound (a)

Phthalocyanine compound (b)

Phthalocyanine compound (c)

Phthalocyanine compound (d)

Phthalocyanine compound (e)

The phthalocyanine compound as described above can be prepared according to a known method for synthesizing a phthalocyanine compound.
The phthalocyanine compound of the general formula (1) according to the present invention is a compound that can be used as an organic dye, and can be used as an optical recording material for forming a recording film of an optical recording medium.
For the purpose of adjusting the hue of the optical recording film and improving the appearance of the appearance, a dye other than the phthalocyanine compound may be added as a part of the optical recording material. The amount of addition can be determined depending on the balance between appearance and recording characteristics. In order to balance the recording characteristics, two or more organic dyes of the general formula (1) may be used, or other dyes such as a phthalocyanine compound not corresponding to the general formula (1) are added and used. However, it is a condition that the added pigment has good light resistance and durability. The composition can be arbitrarily determined in accordance with the balance of attention between reproduction deterioration, light resistance and durability, and recording characteristics other than reproduction deterioration. Even when the appearance and recording characteristics are emphasized, the ratio of the organic dye of the general formula (1) in the total amount of the organic dye to be used needs to be 50% by weight or more, and if it is less than this, recording becomes difficult.

Next, a method for producing an optical recording medium will be described.
It is possible to form an organic dye thin film as an optical recording layer on a substrate by a dry process such as a vacuum deposition method or a sputtering method, but a wet process such as a spin coating method, a dip method, a spray method, A roll coating method or an LB (Langmuir-Blodget) method is also possible. Since the phthalocyanine compound of the general formula (1) of the present invention exhibits high solubility in general-purpose organic solvents such as alcohol solvents, ketone solvents, cellosolve solvents, halogen solvents, hydrocarbon solvents, and chlorofluorocarbon solvents, In view of the properties and uniformity of the recording film, a method of forming a film by spin coating is preferable. Thus, when forming into a film by what is called a coating method, you may add a polymer binder as needed.

Examples of the polymer binder include, but are not limited to, an epoxy resin, an acrylic resin, a polycarbonate resin, a polyester resin, a polyamide resin, a vinyl chloride resin, a nitrocellulose resin, and a phenol resin. The mixing ratio of the polymer binder is not particularly limited, but is preferably 30% by weight or less based on the pigment. The optimum film thickness of the recording layer of the present invention varies depending on the type and combination of the recording film materials, and is not particularly limited, preferably 50 to 300 nm, and more preferably 80 to 150 nm.
The optical recording medium of the present invention is preferably used as a write-once type optical recording medium (CD-R) conforming to a CD format or a CD-ROM format. Such an optical recording medium generally has a structure in which a reflective layer and a protective layer are sequentially laminated on a recording layer on a substrate.

Examples of the film material constituting the reflective layer include metals such as gold, silver, copper, platinum, aluminum, cobalt, and tin, and alloys, oxides, nitrides, and the like based on these metals. Gold or silver is optimal because a high rate is preferred. In some cases, it is also possible to use a highly reflective film of an organic compound. As a method for forming such a reflective film, a dry process such as a vacuum deposition method or a sputtering method is optimal, but is not limited thereto. Although there is no restriction | limiting in particular about the film thickness of a reflecting film, Pillow is preferable and the range of 40-160 nm is preferable.

  Various ultraviolet curable resins can be used as the film material constituting the protective layer, and the film is preferably formed by applying an ultraviolet curable resin by spin coating and curing it by ultraviolet irradiation. It is not limited. When the protective layer is thin, the protective effect is reduced.When the protective layer is thick, the warping and distortion of the disk occur due to shrinkage when the resin is cured, causing deterioration of mechanical properties. Is preferably in the range of 2 to 20 μm.

  By laminating the above-mentioned recording layer, reflective layer and protective layer on the substrate, the resulting disc can be used as an optical recording medium. The disk substrate used in the present invention preferably has a light transmittance of 85% or more for signal writing and reading and a small optical anisotropy. For example, the board | substrate which consists of thermoplastic resins, such as glass, an acrylic resin, a polycarbonate resin, a polyester resin, a polyamide resin, a polystyrene resin, a polyolefin resin, and thermosetting resins, such as an epoxy resin, is mentioned. Among these, those made of a thermoplastic resin are preferable from the viewpoint of easy molding, and those made of an acrylic resin or a polycarbonate resin are particularly preferable from the viewpoint of optical characteristics, mechanical characteristics, and cost.

  The shape of the guide groove of the substrate in the present invention is not particularly limited, and may be trapezoidal, U-shaped or V-shaped. As for the size of the guide groove, the optimum value varies depending on the type of the recording film material and the composition of the recording film, but generally, the half width (width at the half position of the groove depth) is 0.45 to 0.4 mm. A range of 65 μm and a groove depth of 100 to 220 nm is preferable. Since the disc of the present invention needs to function as a CD or CD-ROM after recording information, it complies with the CD or CD-ROM standard (Red Book) and the CD-R standard (Orange Book). It is preferable.

  The optical recording medium according to the present invention can record information by 48 × speed recording, 52 × speed recording or higher speed recording. In the case of 52 × speed recording, the recording linear velocity is in the range of about 20 to 63 m / s, the recording power is in the range of about 15 to 55 mW, and the laser recording power and the recording linear velocity are increased along the circumferential direction. The information is recorded from the center side of the disc toward the outer peripheral side.

  The preparation of the phthalocyanine compound of the present invention, the production and evaluation of the optical recording medium will be described in detail below with reference to examples. In the following description, “part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified.

(Synthesis of organic dye represented by general formula (1))
The organic dye of the present invention can be easily synthesized according to a known method for synthesizing phthalocyanine compounds.
[Phthalocyanine compound (a)]
10 parts of 3-nitrophthalonitrile and 7.4 parts of 2,4-dimethyl-3-pentanol were dissolved in 70 parts of DMF, and this solution was separately prepared using 6.1 parts of t-butoxy sodium and 40 parts of DMF. The solution was added dropwise at a temperature below 0 ° C. Further, 4.8 parts of 80% acetic acid and 17.5 parts of hydrochloric acid were added. Furthermore, 70 kg of water was added dropwise, and the resulting crystals were filtered off. The obtained crystals were washed with water and dried to give 3- (2 ′, 4′-dimethyl-3′-pentoxy) phthalonitrile. 9 parts were obtained.
Ammonia gas was introduced into a solution of 68 parts of quinoline and 2.2 parts of anhydrous aluminum chloride, and 11.9 parts of 3- (2 ′, 4′-dimethyl-3′-pentoxy) phthalonitrile obtained above was added. . The mixture was heated to 180 ° C. and reacted for 2 hours. This was cooled to room temperature and added to precipitate crystals. The produced crystal was separated by filtration, and the crystal was washed with a 47% aqueous methanol solution and dried to obtain 10.3 parts of an aluminum phthalocyanine intermediate.
One part of an aluminum phthalocyanine intermediate was reacted with 0.23 part of dimethylphenylchlorosilane and 0.14 part of triethylamine in 10 parts of 2-butanone at 45 ° C. for 2 hours. The resulting precipitate was filtered off, 20 parts of acetone was added to the obtained filtrate, and 15 parts of ion-exchanged water was further added dropwise to precipitate crystals. The precipitated crystals were separated by filtration, washed with 15 parts of 66% acetone aqueous solution and then dried to obtain 0.7 parts of a phthalocyanine compound (a).
It confirmed that it was a phthalocyanine compound (a) from the result of MS analysis and < ¹ > H-NMR analysis being as follows.
Molecular weight by MS analysis: 1146 Da.
Peak by ¹ H-NMR analysis (deuterated chloroform: DMSO-d ₆ 3: 1 TMS): 9.1 ppm (4H, d), 8.1 ppm (4H, t), 7.7 ppm (4H, d), 6. 5ppm (1H, t), 6.3ppm (2H, t), 5.1ppm (2H, d), 4.7ppm (4H, t), 2.6ppm (8H, m), 1.5ppm (24H, q) ), 1.2 ppm (24H, q), -2.4 ppm (6H, d).

[Phthalocyanine compound (b)]
10 parts of an aluminum phthalocyanine intermediate obtained in the process of synthesizing phthalocyanine compound A was dissolved in 10 parts of trimethyl phosphate. To this solution, 4.5 parts of bromine was added at 30 ° C. and immediately put into 200 parts of water. The green precipitate produced in water was filtered off, and the resulting precipitate was washed with water, dissolved in 150 parts of N-methylpyrrolidone, and 20 parts of an 8% aqueous potassium hydroxide solution were added. Further, 200 parts of water was added dropwise to form a precipitate in the solution, and the precipitate was separated by filtration. The precipitate was washed with water, further washed with methanol and dried to obtain 3.5 parts of brominated aluminum phthalocyanine intermediate.
1 part of brominated aluminum phthalocyanine intermediate was reacted with 0.23 part of dimethylphenylchlorosilane and 0.14 part of triethylamine in 10 parts of 2-butanone at 45 ° C. for 2 hours, and the precipitate formed in the reaction solution was separated by filtration. did. Crystals were precipitated by adding 20 parts of acetone to the filtrate and further dropping 15 parts of ion-exchanged water. The crystals were separated by filtration, washed with 15 parts of 66% acetone aqueous solution and then dried to obtain 0.7 parts of a phthalocyanine compound (b).
From the results of MS analysis and 1H-NMR analysis as follows, it was confirmed that the mixture was mainly a phthalocyanine compound (b) and partly mixed with a phthalocyanine compound (a).
Molecular weights by MS analysis: 1146 Da and 1224 Da.
Peak by ¹ H-NMR analysis (deuterated chloroform: DMSO-d ₆ 3: 1 TMS): 9.1 ppm (3H, d), 8.1 ppm (4H, t), 7.7 ppm (4H, d), 6. 5ppm (1H, t), 6.3ppm (2H, t), 5.1ppm (2H, d), 4.7ppm (4H, t), 2.6ppm (8H, m), 1.5ppm (24H, q) ), 1.2 ppm (24H, q), -2.4 ppm (6H, d).

[Phthalocyanine compound (c)]
A synthesis method similar to that of the phthalocyanine compound (a) except that 0.3 part of diethylphenylchlorosilane obtained by condensing dichlorojetylsilane and phenylmagnesium bromide was used instead of 0.23 part of dimethylphenylchlorosilane. To obtain a phthalocyanine compound (c).
From the results of MS analysis and ¹ H-NMR analysis as follows, it was confirmed that the structure was a phthalocyanine compound (c).
Molecular weight by MS analysis: 1174 Da.
Peak by ¹ H-NMR analysis (deuterated chloroform: DMSO-d ₆ 3: 1 TMS): 9.1 ppm (4H, d), 8.1 ppm (4H, t), 7.7 ppm (4H, d), 6. 5ppm (1H, t), 6.3ppm (2H, t), 5.1ppm (2H, d), 4.7ppm (4H, t), 2.6ppm (8H, m), 1.5ppm (24H, q), 1.2 ppm (24H, q), -1.6 ppm (6H, m), -2.4 ppm (4H, d).

[Phthalocyanine compound (d)]
Synthesis similar to the phthalocyanine compound (a) except that 0.4 part of methylpentylphenylchlorosilane obtained by condensing pentylmethyldichlorosilane and phenylmagnesium bromide was used instead of 0.23 part of dimethylphenylchlorosilane. The method was carried out to obtain the phthalocyanine compound (d).
The results of MS analysis and ¹ H-NMR analysis were as follows, confirming the structure of the phthalocyanine compound (d).
Molecular weight by MS analysis: 1202 Da.
Peak according to ¹ H-NMR analysis (deuterated chloroform: DMSO-d ₆ 3: 1 TMS): 9.1 ppm (4H, d), 8.1 ppm (4H, t), 7.7 ppm (4H, d), 6. 5 ppm (1 H, t), 6.3 ppm (2 H, t), 5.1 ppm (2 H, d), 4.7 ppm (4 H, t), 2.6 ppm (8 H, m), 1.5 ppm (29 H, m) ), 1.2 ppm (24H, q), -0.4 ppm (2H, m), -1.6 ppm (2H, m), -2.4 ppm (5H, m).

[Phthalocyanine compound (e)]
A phthalocyanine compound (a), except that 0.3 part of dimethyl-p-tolylchlorosilane obtained by condensing dichlorodimethylsilane and p-toluylmagnesium bromide was used instead of 0.23 part of dimethylphenylchlorosilane. The same synthesis method was performed to obtain a phthalocyanine compound (e).
From the results of MS analysis and ¹ H-NMR analysis, the structure of phthalocyanine compound E was confirmed.
Molecular weight by MS analysis: 1160 Da.
Peak according to ¹ H-NMR analysis (deuterated chloroform: DMSO-d ₆ 3: 1 TMS): 9.1 ppm (4H, d), 8.1 ppm (4H, t), 7.7 ppm (4H, d), 6. 5ppm (1H, t), 6.3ppm (2H, t), 4.7ppm (4H, t), 2.6ppm (8H, m), 1.9ppm (3H, s), 1.5ppm (24H, q) ), 1.2 ppm (24H, q), -2.4 ppm (6H, d).

(Synthesis of other organic dyes)
[Phthalocyanine compound (f)]
A phthalocyanine compound (f) was obtained in the same manner as the phthalocyanine compound (a) except that triphenylchlorosilane was used instead of methylphenylchlorosilane. The structure of the phthalocyanine compound (f) was confirmed by MS analysis and ¹ H-NMR analysis results.

Phthalocyanine compound (f)

[Phthalocyanine compound (g)]
A phthalocyanine compound (g) was obtained in the same manner as the phthalocyanine compound (a) except that diphenylmethylchlorosilane was used instead of methylphenylchlorosilane. The structure of the phthalocyanine compound (g) was confirmed by MS analysis and ¹ H-NMR analysis results.

Phthalocyanine compound (g)

[Phthalocyanine compound (h)]
A phthalocyanine compound (h) was obtained in the same manner as the phthalocyanine compound (a) except that trimethylchlorosilane was used instead of methylphenylchlorosilane. The structure of the phthalocyanine compound (h) was confirmed by MS analysis and ¹ H-NMR analysis results.

Phthalocyanine compound (h)

(Recording media creation)
[Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-3]
In Examples 1-1 to 1-5, one of phthalocyanine compounds (a) to (e) is used, and in Comparative Examples 1-1 to 1-3, one of phthalocyanine compounds (f) to (h), respectively. In each example, 0.18 g of a phthalocyanine compound was dissolved in 10 ml of a mixed solvent of 1-methoxy-2-propanol / 4-hydroxy-4-methyl-2-pentanone (95: 5 volume ratio), and 0 After passing through a 2 μm filter, using a spin coater, on a polycarbonate substrate having a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 30 mm, having a guide groove having a depth of 200 nm, a half-value width of 530 nm, and a track pitch of 1.6 μm And a recording layer was provided. At this time, the coating amount was adjusted so that the absorbance at the maximum absorption wavelength of the phthalocyanine compound used was 0.50. Next, an Ag film having a thickness of 70 nm was provided on the recording layer to form a reflective layer. Further, a protective layer was provided on this with an ultraviolet curable resin to produce a CD-R disc.
Using this CD-R disc as an optical recording medium, a commercially available CD-R recorder (LTR-52246S; manufactured by ITE-ON) was used for 52-times speed recording, and the recorded disc was a CD-R evaluation apparatus (OMT-2000x4; The recording signal characteristics were evaluated by Pulstec Industrial Co., Ltd. The results are shown in Table 1.

  From Table 1, Examples 1-1 to 1-5 and Comparative Examples using the phthalocyanine compounds (a) to (e) and the phthalocyanine compound (h) having no more than one aromatic ring bonded to silicon as recording materials. It can be seen that the 1-3 optical recording medium has high reflectance and modulation, low BLER, and good recording characteristics. In contrast, in Comparative Example 1-1 using the phthalocyanine compound (f) in which three aromatic rings are bonded to silicon, the sensitivity of the optical recording film is remarkably insufficient, and recording cannot be performed. When the individually bonded phthalocyanine compound (g) is used, the sensitivity is slightly insufficient and the BLER is high. Therefore, it can be seen that it is important that the number of aromatic rings bonded to silicon of the phthalocyanine compound is 1 or less in order to cope with ultrahigh-speed recording at 52 times speed.

[Examples 2-1 to 2-5, Comparative example 2-1]
In Examples 2-1 to 2-5, phthalocyanine compounds (a) to (e) were prepared, and in Comparative Example 2-1, a phthalocyanine compound (h) was prepared. -Dissolved in 10 ml of a mixed solvent of propanol / 1-pentanol (90:10 volume ratio), passed through a 0.2 μm filter, and then, using a spin coater, the depth was 190 nm, the half width was 580 nm, and the track pitch was 1.6 μm. The recording groove was provided on a polycarbonate substrate having a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 30 mm and dried. At this time, the coating amount was adjusted so that the absorbance at the maximum absorption wavelength of the phthalocyanine compound was 0.48. Next, an Ag film having a thickness of 63 nm was provided on the recording layer to form a reflective layer. Further, a protective layer was provided on this with an ultraviolet curable resin to produce a CD-R disc.
Using this CD-R disc as an optical recording medium, a commercially available CD-R recorder (LTR-52246S; manufactured by ITE-ON) was used for 52-times speed recording, and a CD-R evaluation device (DDU-1000; manufactured by Pulstec Industries, Ltd.) ) Was used to measure the reflectance and the degree of modulation of the recorded CD-R disc. Further, on each CD-R disc, the reproduction test was performed 10,000 times at the same location, and then the reflectance and the degree of modulation at the location where the reproduction test was performed were measured using the same evaluation apparatus as described above. The results are shown in Table 2.

  From Table 2, the optical recording medium using the phthalocyanine compounds (a) to (e) in which one aromatic ring is bonded to silicon as the recording material shows almost no change in both reflectance and modulation before and after the reproduction test. However, in the optical recording medium using the phthalocyanine compound (g) in which the aromatic ring is not bonded to silicon, the reflectance is remarkably lowered, and the recorded information cannot be read.

  From the above results, it can be seen that if the number of aromatic rings bonded to silicon of the phthalocyanine compound is 1 or less, ultrahigh-speed recording can be handled, but if it is 0, deterioration due to a reproduction test is severe. Therefore, an optical recording medium capable of recording at ultra-high speed and having sufficient stability at the time of reproduction is only a case of a phthalocyanine compound in which one aromatic ring and two alkyl groups are bonded to silicon. It is clear.

  Since the phthalocyanine compound of the present invention dissolves in a solvent, it can be used for a wide range of oil-soluble organic dyes other than for optical recording media. In particular, it has selective absorption, so it is promising for use as a light absorbing / blocking material, color filter dyes, ink jet dyes, and sensitizing dyes for solar cells, and is also a phthalocyanine. Therefore, it can be applied as various catalysts.

Claims (6)

A phthalocyanine compound represented by the following general formula (1).
General formula (1)

[Wherein, X1 to X4 may be the same or different, and each may have an alkyl group that may have a substituent, an aryl group that may have a substituent, or an cycloalkyl that may have a substituent. Group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a substituent Represents an organic group selected from the group consisting of an alkylthio group which may have an arylthio group and an arylthio group which may have a substituent.
Yl to Y4 may be the same or different and each represents an organic group selected from the group consisting of a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, and a sulfonamide group.
R1 and R2 may be the same or different and each represents an alkyl group which may have a substituent.
Ar represents an aromatic ring which may have a substituent.
m1, m2, m3, m4, n1, n2, n3, and n4 each represents an integer of 0 to 4, and may be the same or different. m1 + n1, m2 + n2, m3 + n3, m4 + n4 are It may be the same or different. ] The phthalocyanine compound according to claim 1, wherein at least one of X1 to X4 is an alkyl group which may have a substituent or an alkoxy group which may have a substituent. The phthalocyanine compound according to claim 2, wherein m1 is 0 or 1, m2 to m4 are 0, and when m1 is 1, Y1 is a halogen atom. The phthalocyanine compound according to any one of claims 1 to 3, wherein Ar is a phenyl group or a p-tolyl group, and R1 and R2 are each one of a methyl group, an ethyl group, and a pentyl group. . The organic pigment | dye containing at least 1 sort (s) of the phthalocyanine compound in any one of Claims 1-4. An optical recording medium comprising at least one phthalocyanine compound according to any one of claims 1 to 4 on a substrate.