JPH0624145A - Optical recording medium and manufacture thereof - Google Patents

Abstract

PURPOSE:To improve the sensitivity and heat resistance of a near infrared band by containing organic dyestuffs shown in specified general formula in a recording layer in an optical recording medium, which is recorded by a recording blank proper to information recording by laser beams and can be regenerated. CONSTITUTION:Polymethylene dyestuffs having structure shown in formula are contained in a recording layer. R0-R5 in formula represent a hydrogen atom or a monovalent organic residue, and at least one of R0-R3 represents the monovalent organic residue having one fluorine atom. (m) represents 0-2, and X<theta> represents an anion residue. The monovalent organic residue having the fluorine atom represents a substituted or non-substituted alkyl group having the fluorine atom, an alkenyl group, an aralkyl group and an aryl group. Fluorine atomicity at a time when the number of carbon is represented by (n) may also be 0.1n to 3n or be 0.5n to 1.8n in the monovalent organic residue having the fluorine atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium, and more particularly to a record blank suitable for recording information by laser light, particularly semiconductor laser light, and information capable of optically reproducing information recorded by laser light. It's about records.

[0002]

2. Description of the Related Art Optical recording media such as optical disks and optical cards generally have small (for example, about 1 μm) optically detectable pits formed in a spiral, concentric or linear shape on a recording layer formed on a substrate. Information can be stored at a high density by recording in the manner that tracks are formed.

As a method of optically recording, for example, optical engineering (Opti
Cal Engineering), Volume 15, No. 2, 3
March-April, 1976 99
As described on the page, by irradiating the recording layer of the optical recording medium with a light beam, for example, a laser beam, a type that causes deformation or holes in the recording layer, a type that forms bubbles, or a phase change, discoloration, or decolorization The type etc. which give rise to etc. are known.

As a material used for a recording layer of an optical recording medium for performing such recording, for example, an inorganic substance such as a metal thin film such as an aluminum vapor deposition film, a bismuth thin film, a tellurium oxide thin film or a chalcogenite type amorphous glass film is used. Those mainly using are proposed. Since these thin films are generally sensitive to light having a wavelength in the vicinity of 350 to 800 nm and have high reflectance for laser light, they have drawbacks such as low utilization of laser light.

Further, such an inorganic substance is usually formed into a recording layer by a method such as vapor deposition or sputtering, but such a film forming method requires a large-scale production line equipped with a vacuum system, which results in cost reduction. There was also a drawback in lowering.

For these reasons, in recent years, vigorous research has been conducted on optical recording media using organic dye compounds capable of changing optical physical properties with light energy of a relatively long wavelength (for example, 780 nm or more). ing. An optical recording medium using such an organic dye has an oscillation wavelength of 780 nm, for example.
Alternatively, it is effective in that pits can be formed by a semiconductor laser having a wavelength of around 830 nm. Furthermore, since the organic dye can be formed into a film by wet coating and is easy to handle, industrial mass production is easy and the facility cost can be reduced.

[0007] And, the applicant of the present application, USP 5,079,
No. 127 and USP 4,944,981 disclose a polymethine dye capable of recording with a high S / N ratio by a semiconductor laser and having good thermal stability, which gives an optical recording medium.

However, in recent years, due to the downsizing of recording / reproducing devices, the temperature inside the devices tends to rise, and in recent years, optical recording media of the type carried by individuals such as optical cards have been developed. Such an optical recording medium is not necessarily used only in an air-conditioned office,
It is also necessary to consider the situation of being left in a high temperature environment for a long time, and there is a demand for an optical recording medium that is more excellent in stability in a high temperature environment.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation as described above, and an object thereof is to have excellent sensitivity to light in the near infrared region and to further improve heat resistance. An object is to provide an excellent optical recording medium.

Another object of the present invention is to provide a method for producing an optical recording medium having high recording sensitivity and heat resistance with high productivity.

[0011]

That is, the optical recording medium of the present invention is characterized by having a recording layer containing an organic dye represented by the following general formula (I).

[0012]

[Outside 14] (In the formula, R _{0 to} R ₅ are hydrogen atoms or monovalent organic residues, and at least one of R _{0 to} R ₃ is a monovalent organic residue having a fluorine atom. M is 0, 1 Or 2,

[0013]

[Outside 15] Indicates an anion residue. )

The optical recording medium of the present invention has the following general formula (I
It is characterized by having a recording layer containing the polymethine dye represented by I).

[0015]

[Outside 16] (In the formula

[0016]

[Outside 17] Represents an anion residue, and R ₀ ′ to R ₃ ′ are R ₀ ′ and R
₁ ′ and at least one combination of R ₂ ′ and R ₃ ′ is N
Together with a substituted or unsubstituted pyrrolidine ring having a fluorine atom, a substituted or unsubstituted piperidine ring having a fluorine atom, a substituted or unsubstituted morpholine ring having a fluorine atom, a substituted or unsubstituted tetrahydropyridine ring having a fluorine atom Or a substituted or unsubstituted cyclohexylamine ring having a fluorine atom represented by the following formula,

[0017]

[Outside 18] Represents a group of atoms necessary for forming a hydrogen atom, other represents a hydrogen atom or a monovalent organic residue, and R ₄ ′ and R ₅ ′ represent a hydrogen atom or a monovalent organic residue. m is 0, 1 or 2. )

The method for producing an optical recording medium of the present invention is a method for producing an optical recording medium having a recording layer containing an organic dye represented by the following general formula (I), wherein The recording layer is formed by applying a coating liquid containing an organic dye represented by the above on a substrate.

[0019]

[Outside 19] (In the formula, R _{0 to} R ₅ are hydrogen atoms or monovalent organic residues, and at least one of R _{0 to} R ₃ is a monovalent organic residue having a fluorine atom. M is 0, 1 Or 2,

[0020]

[Outside 20] Indicates an anion residue. )

Further, the method for producing an optical recording medium of the present invention is a method for producing an optical recording medium having a recording layer containing an organic dye represented by the following general formula (II), which is represented by the following general formula (II). It is characterized in that the recording layer is formed by applying a coating liquid containing the organic dye shown on the substrate.

[0022]

[Outside 21] (In the formula

[0023]

[Outside 22] Represents an anion residue, and R ₀ ′ to R ₃ ′ are R ₀ ′ and R
₁ ′ and at least one combination of R ₂ ′ and R ₃ ′ is N
Together with a substituted or unsubstituted pyrrolidine ring having a fluorine atom, a substituted or unsubstituted piperidine ring having a fluorine atom, a substituted or unsubstituted morpholine ring having a fluorine atom, a substituted or unsubstituted tetrahydropyridine ring having a fluorine atom Or a substituted or unsubstituted cyclohexylamine ring having a fluorine atom represented by the following formula,

[0024]

[Outside 23] Represents a group of atoms necessary for forming a hydrogen atom, other represents a hydrogen atom or a monovalent organic residue, and R ₄ ′ and R ₅ ′ represent a hydrogen atom or a monovalent organic residue. m is 0, 1 or 2. )

The present invention will be described in detail below. The optical recording medium of the present invention is characterized by containing a polymethine dye having a structure represented by the following general formula (I).

[0026]

[Outside 24]

In the above general formula (I), R _{0 to} R ₅ represent a hydrogen atom or a monovalent organic residue, and in the present invention, at least one of the substituents R _{0 to} R ₃ is a fluorine atom. A monovalent organic residue having an atom (hereinafter abbreviated as R _F ) is preferable. By using at least one of R _{0 to} R ₃ as R _F , a polymethine dye having more excellent heat resistance than conventional ones can be obtained, and by incorporating such a polymethine dye in the recording layer, heat resistance can be improved. It is possible to obtain an excellent optical recording medium.

Specific examples of R _F suitably used for R _{0 to} R ₃ in the present invention include, for example, a substituted or unsubstituted alkyl group having a fluorine atom and a substituted or unsubstituted alkenyl group having a fluorine atom. A substituted or unsubstituted aralkyl group having a fluorine atom, a substituted or unsubstituted aryl group having a fluorine atom, and the like.

In the present invention, as an explanation of R _F , for example, “unsubstituted aryl group having a fluorine atom” means
A phenyl group means one that is not substituted by another element or an organic residue except that one or more hydrogen atoms are substituted by a fluorine atom, and it is a "substituted aryl group having a fluorine atom". Is, for example, one or more hydrogen atoms in the phenyl group are replaced by fluorine atoms, and one or more hydrogen atoms in the phenyl group are other elements or monovalent organic residues. Substituted, or one or more hydrogen atoms in the phenyl group are substituted with a monovalent organic residue having a fluorine atom.

Next, R _{F in the} present invention will be described in more detail. Examples of the unsubstituted alkyl group having a fluorine atom include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group and 1-fluoro. Ethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 2,2-difluoroethyl group, 1,1,1-trifluoroethyl group, 1,
1,2-trifluoroethyl group, 1,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,1,2-tetrafluoroethyl group, pentafluoroethyl group , 1-fluoropropyl group, 2-fluoropropyl group, 3-fluoropropyl group, 1,1-difluoropropyl group, 1,2-difluoropropyl group,
1,3-difluoropropyl group, 2,2-difluoropropyl group, 2,3-difluoropropyl group, 3,3-difluoropropyl group, 1,1,2-trifluoropropyl group, 1,1,3-tri Fluoropropyl group, 1,2,
2-trifluoropropyl group, 1,2,3-trifluoropropyl group, 1,3,3-trifluoropropyl group,
2,2,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,3,3-tetrafluoropropyl group, 1, 1,2,3-tetrafluoropropyl group,
1,2,2,3-tetrafluoropropyl group, 1,2,
3,3-tetrafluoropropyl group, 2,2,3,3-
Tetrafluoropropyl group, 1,3,3,3-tetrafluoropropyl group, 2,3,3,3-tetrafluoropropyl group, 1,1,2,2,3-pentafluoropropyl group, 1,1, 2,3,3-pentafluoropropyl group, 1,1,3,3,3-pentafluoropropyl group,
1,2,2,3,3-pentafluoropropyl group, 1,
2,3,3,3-pentafluoropropyl group, 2,2
3,3,3-pentafluoropropyl group, 1,1,2,
2,3,3-hexafluoropropyl group, 1,1,2,
3,3,3-hexafluoropropyl group, 1,2,2
3,3,3-hexafluoropropyl group, heptafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, heptafluoro-2-propyl group, 2,2-difluorobutyl group Group, 2,2,3,3-tetrafluorobutyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group,
2,2,4,4,4-pentafluorobutyl group, 2,
2,3,4,4,4-hexafluorobutyl group, 1,
2,3,4-tetrafluorobutyl group, nonafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,1,3,3,4,4,4 -Heptafluoro-2-butyl group, t-nonafluorobutyl group,
5,5,5-trifluoropentyl group, 4,4,5,
5,5-pentafluoropentyl group, 3,3,5,5,
5-pentafluoropentyl group, 3,3,4,4-tetrafluoropentyl group, 1,2,3,4,5-pentafluoropentyl group, 2,2,3,3,4,4,5,5 −
Octafluoro-1-pentyl group, 1,1,2,2
3,3,4,4-octafluoropentyl group, 6,6
6-trifluorohexyl group, 6,6,7,7,7-pentafluoropentyl group, 8,8,8-trifluorooctyl group, 5,5,6,6,7,7,8,8-octa Examples thereof include a fluorooctyl group.

Further, as another alkyl group containing a fluorine atom, for example, a substituted alkyl group containing a fluorine atom, for example, a 2-hydroxy-2-fluoroethyl group, 2
Fluorine-containing hydroxyalkyl groups such as hydroxy-1,1 difluoroethyl group and 3-hydroxy-2,2-difluoropropyl group, 2-acetoxy-2 fluoroethyl group, 2-acetoxy-2,2-difluoroethyl group, 3
-Fluorine-containing acetoxyalkyl group such as acetoxy-2,2,3,3-tetrafluoropropyl group, 2-carboxy-1,2-difluoroethyl group, 3-carboxy-
Fluorine-containing carboxyalkyl group such as 3-fluoropropyl group, 4-carboxy-2,2-difluorobutyl group, trifluoromethoxymethyl group, trifluoromethoxyethyl group, trifluoromethoxy-2-difluoroethyl group, difluoromethoxyethyl group Group, 2-trifluoroethoxy-2'-difluoroethyl group, trifluoromethoxy-n-propyl group, pentafluoroethoxyethyl group, pentafluoroethoxypropyl group, methoxy-3,3-difluoropropyl group, trifluoromethoxy And fluorine-containing alkoxyalkyl groups such as an octyl group.

Next, as the unsubstituted alkenyl group having a fluorine atom, for example, trifluoroethylene group, 2,2
-Difluoroethylene group, pentafluoropropenyl group, heptafluorobutenyl group and the like, and examples of the substituted alkenyl group having a fluorine atom include 2-
A hydroxy-3,3-difluoropropenyl group etc. are mentioned.

Examples of the unsubstituted aralkyl group having a fluorine atom include p-fluorobenzyl group, m-fluorobenzyl group, pentafluorobenzyl group, p-trifluoromethylbenzyl group, 1- (pentafluorophenyl) ethyl group. Group, a 3- (pentafluorophenyl) propyl group, and the like.

Examples of the substituted aralkyl group having a fluorine atom include 4-hydroxy-3-fluorobenzyl group and the like. Further, examples of the unsubstituted aryl group having a fluorine atom include p-fluorophenyl group and pentafluorophenyl group, and examples of the substituted aryl group having a fluorine atom include p-trifluoromethyl-
Examples thereof include a phenyl group and a 3,5-bis (trifluoromethyl) -phenyl group.

In the present invention, in order to improve the heat resistance of the optical recording medium, at least one of R _{0 to} R _{3 in} the organic dye represented by the general formula (I) is used as described above. R _F
In particular, at least _one of R ₀ and R ₁ and at least one of R ₂ and R ₃ is R _F, and further, the polymethine dye in which R _{0 to} R ₃ are all R _F is The heat resistance of the recording medium can be improved, and the solubility of the dye in an organic solvent can be improved, which is preferable for mass-producing optical recording media having excellent heat resistance.

In the present invention, R _F out of R _{0 to} R ₃ is
Remaining substituents other than the A, may be a monovalent organic residue other than a hydrogen atom or R _F, as the monovalent organic residue other than this case R _F, an alkyl group (e.g., methyl , Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group,
n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group and the like), and further other alkyl groups such as a substituted alkyl group, for example, a 2-hydroxyethyl group, 3-hydroxypropyl, 4
-Hydroxyalkyl group such as hydroxybutyl group, 2
-Acetoxyethyl group, acetoxyalkyl group such as 2-acetoxyprol group, carboxymethyl group, 2-carboxyethyl group, carboxyalkyl group such as 3-carboxypropyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, Examples of aralkyl groups such as methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, and propoxymethyl group, and other aralkyl groups include benzyl group, p-chlorobenzyl group, p-methylbenzyl group. ,
2-phenylmethyl group, 2-phenylpropyl group, 3-
Examples thereof include a phenylpropyl group, an α-naphthylmethyl group, a β-naphthylethyl group and the like, and further, a substituted or unsubstituted aryl group (for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a methoxyphenyl group, a dimethoxyphenyl group. Group, trimethoxyphenyl group, ethoxyphenyl group, dimethylaminophenyl group, diethylaminophenyl group, dipropylaminophenyl group, dibenzylaminophenyl group, diphenylaminophenyl group, ditolylaminophenyl group, etc.).

In the present invention, when at least two of R _{0 to} R ₃ are R _F , R _F may be the same or different.

[0038] Also At a present invention, as R _F, when the number of carbon atoms of R _F is n, when more than 0.1n the number of fluorine atoms 3n below were particularly 0.5n or 1.8n or less ,
The heat resistance of the optical recording medium can be improved and the solubility of the dye in an organic solvent can be improved, which is preferable in mass production of the optical recording medium having excellent heat resistance.

Furthermore, in the present invention, various R _F described above are used.
Of these, a substituted or unsubstituted alkyl group having a fluorine atom is particularly preferable as an organic residue for satisfying both the two effects of improving the heat resistance of the optical recording medium and improving the solubility of the organic dye in an organic solvent. Is. Further, in this case, the number of carbon atoms of the alkyl group is preferably 1 to 8, particularly preferably 1 to 5.

As R ₄ and R ₅ , a monovalent organic residue containing R _F or a hydrogen atom can be mentioned. As R _F , the above-mentioned monovalent organic residue having a fluorine atom can be used. As the monovalent organic residue other than R _F , a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group (for example,
Phenyl group, naphthyl group, tolyl group, xylyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group, dimethylaminophenyl group, diethylaminophenyl group, dipropylaminophenyl group, dibenzylaminophenyl group, Diphenylaminophenyl group, ditolylaminophenyl group, etc.),
A substituted or unsubstituted heterocyclic group (for example, a pyridyl group,
Quinolyl group, lepidyl group, methylpyridyl group, furyl group, thienyl group, indolyl group, pyrrole group, carbazolyl group, N-ethylcarbazolyl group, etc., or substituted or unsubstituted styryl group, (for example, styryl group, Methoxystyryl group, dimethoxystyryl group, trimethoxystyryl group, ethoxystyryl group, dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group, dibenzylaminostyryl group, diphenylaminostyryl group, 2,2-diphenylvinyl group Two
-Phenyl-2-methylvinyl group, 2- (dimethylaminophenyl) -2-phenylvinyl group, 2- (diethylaminophenyl) -2-phenylvinyl group, 2- (dibenzylaminophenyl) -2-phenylvinyl group , 2,
2-di (diethylaminophenyl) vinyl group, 2,2-
(Methoxyphenyl) vinyl group, 2,2- (ethoxyphenyl) vinyl group, 2- (dimethylaminophenyl)-
2-methylvinyl group, 2- (diethylaminophenyl)
2-ethylvinyl group) and the like can be used.

Further, at least one of R ₄ and R ₅ may be an amino-substituted aryl group represented by the following formula (III), in which at least one of R ₆ and R ₇ is R _{F. In} this case, optical recording The heat resistance of the medium can be further improved.

[0042]

[Outside 25] (However, R ₆ and R ₇ are a hydrogen atom or a monovalent organic residue, and at least one of R ₆ and R ₇ is R _F. )

However, considering heat resistance of the optical recording medium and mass productivity of the recording layer by wet coating, R ₄ and R ₅ are monovalent organic residues other than R _F , and R ₄ and At least one of R ₅ is preferably a substituted or unsubstituted aryl group, and when at least one of R ₄ and R ₅ is R _F , it is an amino-substituted aryl group represented by the above formula (III). In addition, it is preferable that at least one of R ₆ and R ₇ , particularly both of them, be a substituted or unsubstituted methyl group or ethyl group having a fluorine atom.

That is, by using a polymethine dye compound having R ₄ and R ₅ as the above-mentioned organic residues in the recording layer, an optical recording medium having excellent heat resistance can be obtained, and such a compound has excellent solvent solubility. Therefore, mass productivity of a high-quality optical recording medium having a low noise level can be improved.

The second optical recording medium of the present invention is characterized by containing a polymethine dye represented by the following general formula (II).

[0046]

[Outside 26]

In the general formula (II), at least one of R ₀ ′ to R ₃ ′, which is a combination of R ₀ ′ and R ₁ ′ and R ₂ ′ and R ₃ ′, has a fluorine atom together with N. A substituted or unsubstituted pyrrolidine ring, a substituted or unsubstituted piperidine ring having a fluorine atom, a substituted or unsubstituted morpholine ring having a fluorine atom, a substituted or unsubstituted tetrahydropyridine ring having a fluorine atom or represented by the following formula A substituted or unsubstituted cyclohexylamine ring having a fluorine atom,

[0048]

[Outside 27] By making the atomic group necessary to form a polymethine dye, a polymethine dye having excellent heat resistance can be obtained. In addition, R
_{In 0} ′ to R ₃ ′, the remaining substituents which do not form a ring are represented by R
_{The use of F} is preferable in order to improve the heat resistance of the polymethine dye, but it may be, for example, a hydrogen atom or a monovalent organic residue other than R _F. Here, as R _F can be used various R _F mentioned above, also as the monovalent organic residue other than R _F, an alkyl group (e.g., methyl group, ethyl group, n- propyl group, iso -Propyl group, n-butyl group, iso-butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group,
t-octyl group), and other alkyl groups, for example, substituted alkyl groups include, for example, hydroxyalkyl groups such as 2-hydroxyethyl group, 3-hydroxypropyl and 4-hydroxybutyl group, 2-acetoxyethyl group. Group, acetoxyalkyl group such as 2-acetoxypropyl group, carboxymethyl group, 2-carboxyethyl group, carboxyalkyl group such as 3-carboxypropyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, Aralkyl groups (eg, benzyl group, p-chlorobenzyl group, p-methylbenzyl group, 2-phenylmethyl group) such as alkoxyalkyl groups such as ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, and propoxymethyl group. , 2-pheny Propyl, 3-phenylpropyl, alpha-naphthylmethyl group, beta-naphthylethyl group)
Further, a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, tolyl group, xylyl group, methoxyphenyl group, dimethoxyphenyl group,
And a trimethoxyphenyl group, an ethoxyphenyl group, a dimethylaminophenyl group, a diethylaminophenyl group, a dipropylaminophenyl group, a dibenzylaminophenyl group, a diphenylaminophenyl group, a ditolylaminophenyl group).

In the polymethine dye represented by the general formula (II), R ₄ ′ and R ₅ ′ include a monovalent organic residue containing R _F or a hydrogen atom, and R _{F is} as described above. A monovalent organic residue having a fluorine atom can be used, and as the monovalent organic residue other than R _F , a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted In addition to the unsubstituted aryl group,
A substituted or unsubstituted heterocyclic group (for example, a pyridyl group,
Quinolyl group, lepidyl group, methylpyridyl group, furyl group, thienyl group, indolyl group, pyrrole group, carbazolyl group, N-ethylcarbazolyl group, etc., or substituted or unsubstituted styryl group (for example, styryl group, methoxy group Styryl group, dimethoxystyryl group, trimethoxystyryl group, ethoxystyryl group, dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group, dibenzylaminostyryl group, diphenylaminostyryl group, 2,2-diphenylvinyl group, 2-
Phenyl-2-methylvinyl group, 2- (dimethylaminophenyl) -2-phenylvinyl group, 2- (diethylaminophenyl) -2-phenylvinyl group, 2- (dibenzylaminophenyl) -2-phenylvinyl group, 2, 2
-Di (diethylaminophenyl) vinyl group, 2,2-di (methoxyphenyl) vinyl group, 2,2- (ethoxyphenyl) vinyl group, 2- (dimethylaminophenyl)-
2-methylvinyl group, 2- (diethylaminophenyl)
2-ethylvinyl group) and the like can be used.

At least one of R ₄ ′ and R ₅ ′ may be an amino-substituted aryl group represented by the following formula (IV), in which at least one of R ₆ ′ and R ₇ ′ is R _F.

[0051]

[Outside 28] However, R ₆ ′ and R ₇ ′ are a hydrogen atom or a monovalent organic residue, and at least one of R ₆ ′ and R ₇ is R _F.

Further, at least one of R ₄ 'and R ₅ ' may be an amino-substituted aryl group represented by the following formula (V).

[0053]

[Outside 29] Wherein R ₈ ′ and R ₉ ′ are a combination of R ₈ ′ and R ₉ ′ with N, and a substituted or unsubstituted pyrrolidine ring having a fluorine atom, a substituted or unsubstituted piperidine ring having a fluorine atom, a fluorine atom. A substituted or unsubstituted morpholine ring having, a substituted or unsubstituted tetrahydropyridine ring having a fluorine atom, or a substituted or unsubstituted cyclohexylamine ring having a fluorine atom represented by the following formula,

[0054]

[Outside 30] Is a group of atoms necessary to form.

[0055] The monovalent organic residue having a heterocyclic ring having R _F, or a fluorine atom in at least one of R ₄ 'and R _5' to at least one of or a R _F, also R ₄ 'and R _5' The compound of the general formula (II)
It is preferable for improving the heat resistance of the polymethine dye. However, in consideration of heat resistance of the optical recording medium and mass productivity by wet coating of the recording layer, R ₄ ′ and R ₅ ′ are monovalent organic residues other than R _F and are R ₄ ′ and R ₄ ′.
'It is preferable to be substituted or unsubstituted aryl group at least one of, and R _{4' 5} at least one of and R ₅ 'in the case of the R _F is an amino substituted aryl group represented by the formula (IV) And at least one of R ₆ and R ₇ is a substituted or unsubstituted methyl group or ethyl group having a fluorine atom, particularly at least both, or is an amino-substituted aryl group represented by the above formula (V). And R ₈ ′ and R ₉ ′ together with N in the combination of R ₈ ′ and R ₉ ′, a methyl group in which one or more hydrogen atoms are replaced by fluorine atoms (hereinafter referred to as fluorine-substituted methyl group). Abbreviated), pyrrolidine ring substituted with fluorine-substituted methyl group, piperidine ring substituted with fluorine-substituted methyl group, morpholine ring substituted with fluorine-substituted methyl group, tetrahydropyridine ring substituted with fluorine-substituted methyl group, It is preferable that the atomic group necessary for forming a cyclohexylamine ring substituted with a hydrogen-substituted methyl group. That is, an optical recording medium having excellent heat resistance can be obtained by using a polymethylene dye compound having R ₄ ′ and R ₅ ′ as the above organic residues in the recording layer, and such a compound has excellent solvent solubility. In addition, it is possible to improve the mass productivity of a high-quality optical recording medium having a low noise level.

Further, in the polymethine dye represented by the general formula (I) or (II),

[0057]

[Outside 31] Is chlorine ion, bromine ion, iodine ion, perchlorate ion, nitrate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion, ethylsulfate ion, propylsulfate ion, tetra Fluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfonate ion, acetate ion, trifluoroacetate ion, propionacetate ion, benzoate ion, oxalate ion , Succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chloro Sulfonate ion, fluorosulfonate ion, trifluoromethanesulfone Indicating salt ions, hexafluoroarsenate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion, zirconate ion, an anion, such as.

Specific examples of the polymethine dye compound represented by the above general formulas (I) and (II) used in the present invention are listed below in Tables 1-1 and 1-2.
It is not limited to these.

The specific examples shown below are simplified and shown as follows. That is, when the polymethine dye has, for example, the following structures (A) and (B),

[0060]

[Outside 32] Each is shown below.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

[0068]

[Table 8]

The polymethine dye compound according to the present invention can be produced by S. “Journal of American Chemical Society” by BS Wildi et al.
80, 3772-37.
77, 1958, H. Schmid (H. Schmid
T. et al., “Liebig Annalendel Chemie (Ann)” 623, 204-216, 1959, or R.H. R. Wilzinger
Et al., "Helvetica Shimika Actor (Helv.
Chim. Acta. ) ”24, 369, 1941 and the like.

The optical recording medium of the present invention, as shown in FIG.
It can be formed by providing the recording layer 2 containing the polymethine dye compound represented by the general formula (I) or (II) on the substrate 1.

As the substrate 1, plastics such as polycarbonate, polyester, acrylic resin, polyolefin resin, phenol resin, epoxy resin, polyamide and polyimide, glass or metals can be used.

In forming the recording layer 2, the polymethine dye compound represented by the general formula (I) or (II) may be used alone or in combination of two or more, and further other dyes such as the general formula ( I) or (II)
In the polymethine system other than the polymethine dye compound shown in,
Naphtholactam type, azulene type, pyrylium type, squalium type, croconium type, triphenylmethane type, xanthene type, anthraquinone type, cyanine type, phthalocyanine type, dioxazine type, tetrahydrocholine type, triphenothiazine type, phenanthrene type, or metal and metal Compounds such as Al, Te, Bi, Sn, I
_{n, Se, SnO, TeO 2} , As, may be mixed dispersed or stacked such as Cd.

Further, in order to improve the light resistance of the recording layer 2, a stabilizer may be mixed in the recording layer 2. As the stabilizer, various metal chelate compounds, particularly Zn, Cu and N.
i, Cr, Co, Mn, Pd, Zr as the central metal, and polydentate ligands such as N ₄ , N ₂ O ₂ , N ₂ S ₂ S ₄ ,
Those having tetradentate ligands such as O ₂ S ₂ and O _4, etc., or combinations thereof, various aromatic amines, diamines and nitrogen-containing aromatic compounds, and onium salts thereof, for example, aminium salts, diimonium salts, Pyridinium salts, imidazolinium salts, quinolium salts and the like can be mentioned. Furthermore, a pyrylium salt, which is an oxygen-containing aromatic salt, or the like is also used.

Particularly, the aminium salt represented by the following general formula (IV) and the diimonium salt represented by the following general formula (V) have good compatibility with the polymethine compound when the recording layer is produced by wet coating, It is possible to obtain a higher performance optical recording medium having excellent durability and light resistance.

[0075]

[Outside 33] (However, A is

[0076]

[Outside 34] And R _{8 to} R ₁₅ are substituents having 1 to 8 carbon atoms,

[0077]

[Outside 35] Indicates an anion. )

[0078]

[Outside 36] (However, R _{16 to} R ₂₃ are a substituent having 1 to 8 carbon atoms,

[0079]

[Outside 37] Indicates an anion. ) And, the addition amount of these stabilizers in the recording layer to the polymethine dye as the optical recording material is as follows.

[0080]

[Outside 38] Is preferred.

Further, in the aminium salt compound represented by the general formula (IV), at least one of R _{8 to} R ₁₅ is
When one is an alkoxyalkyl group, an alkenyl group or an alkynyl group, the solubility of the aminium salt compound in a solvent can be improved, and the recording layer of the optical recording medium of the present invention is formed using a wet coating method. It is preferably used in some cases.

For the same reason, in the diimonium salt compound represented by the general formula (V), it is preferable that at least one of R _{16 to} R ₂₃ is an alkoxyalkyl group, an alkenyl group or an alkynyl group.

The recording layer 2 is formed on the substrate 1 by various methods such as a wet coating method or a vapor deposition method such as a vapor deposition method. In particular, the wet coating method is intended to reduce the cost of the optical recording medium. Is the preferred method.

When the wet coating method is used, it can be formed by coating the substrate 1 with a solution in which a polymethine compound is dissolved or dispersed in an organic solvent. It is also possible to form a film by mixing a binder in the recording layer in consideration of coating film stability.

The organic solvent that can be used for wet coating varies depending on whether the above-mentioned polymethine compound is in a dispersed state or in a dissolved state, but is generally an alcohol type, a ketone type, an amide type, an ether type or an ester type. It is possible to use a solvent such as a system, an aliphatic halogenated hydrocarbon system, an aromatic system, an aliphatic hydrocarbon system, or a fluorine system, and a solvent excellent in the solubility of the polymethine compound of the present invention is particularly preferred.

On the other hand, in the case of direct wet coating on a resin substrate, an organic solvent that does not dissolve the surface of the resin substrate or cause cracks on the surface of the resin substrate is used among the above organic solvents. is necessary.

However, since the polymethine compound according to the present invention is excellent in solvent solubility, the range of choice of coating solvent or substrate material is wider than before even when an organic dye is coated by wet coating on a resin substrate. At the same time, the conditions for producing an excellent optical recording medium having a low noise level can be relaxed more than before.

Examples of the binder include nitrocellulose, ethylcellulose, polystyrene, polyvinylpyrrolidone, polymethylmethacrylate, polyamide and the like. Also, if necessary,
Waxes, higher fatty acids and amides (eg oleylamide) can be used as additives.

To the above binders, plasticizers such as dioctyl phthalate, dibutyl phthalate and tricresyl phosphate, oil agents such as mineral oil and vegetable oil, dispersants such as sodium alkylbenzene sulfonate and polyoxyethylene alkylphenyl ether, and other additives. By appropriately mixing the agents, the film forming property of the recording layer and the coating film stability can be improved.

The coating is carried out using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a Meyer bar coating method, a blade coating method, a curtain coating method, a roller coating method or a gravure coating method. It can be carried out.

The content of the polymethine compound in the recording layer 2 is 1% or more and is usually 40 to 100% by weight, preferably 50 to 100% by weight.
100% by weight is desirable. When it is 40% by weight or more, it is possible to obtain sufficient light absorption of the recording layer and sufficient light reflectance for the reproduction laser beam.

The thickness of the recording layer 2 is 100Å to 20 μm.
m, preferably 200Å to 1 μm. In addition,
If it is possible to stably form a thin film having sufficient light reflectivity for the recording laser light, it is preferable that the thin film be as thin as possible.

Further, in the optical recording medium of the present invention, as shown in FIG. 2, a protective layer 3 which is transparent to recording and reproducing laser light can be provided on the recording layer 2. The protective layer 3 is
When light is irradiated from the substrate 1 side, it may be opaque.

Further, as shown in FIG. 3, an undercoat layer 4 may be provided between the substrate 1 and the recording layer 2.

Further, as shown in FIG. 4, it is possible to use both the protective layer 3 and the undercoat layer 4.

The undercoat layer has (a) improved adhesion, (b) water or gas barrier, (c) improved storage stability of the recording layer, (d) improved reflectance, and (e) solvent It is provided for the purpose of protecting the substrate, and (f) forming pregrooves. For the purpose of (a), polymer materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, and various substances such as silane coupling agents are used. For the purposes of (b) and (c), in addition to the above polymeric materials, inorganic compounds such as SiO ₂ , MgF ₂ , S
Metals or metalloids such as iO, TiO ₂ , ZnO, TiN, SiN, eg Zn, Cu, S, Ni, Cr, G
e, Se, Cd, Ag, Al or the like can be used. For the purpose of (d), a metal such as Al or Ag, or an organic thin film having a metallic luster such as a cyanine dye or a methine dye can be used. For the purposes (e) and (f), an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin or the like can be used. The thickness of the undercoat layer is 50Å to 100 μm, preferably 200Å
30 μm is suitable.

The protective layer is provided for the purpose of protecting it from scratches, dust, dirt, etc., and improving the storage stability and reflectance of the recording layer. The same material as that for the undercoat layer is used as the material. can do. The thickness of the protective layer is 1
A value of 00 Å or more, preferably 1000 Å or more is suitable.

At this time, the polymethine dye compound of the general formula (I) of the present invention may be contained in the undercoat layer and / or the protective layer. Further, a stabilizer in the undercoat layer or the protective layer,
A dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer and the like may be contained.

Further, as another constitution of the optical recording medium according to the present invention, the recording layer 2 using two recording mediums of the same constitution shown in FIGS. 1 to 4 (in some cases, one of them is only a substrate) is used. It may be a so-called air sandwich structure in which is placed inside and sealed, or a so-called close contact structure (bonding structure) in which the layers are adhered via the protective layer 3.

The thus-produced optical recording medium of the present invention (a record blank in which no information is recorded) is irradiated with modulated electromagnetic radiation for recording to bleach or discolor the recording layer 2. Information is recorded by forming recesses (pits).

In particular, the optical recording medium of the present invention can be recorded by irradiation with a gas laser such as a helium-neon laser (oscillation wavelength 633 nm), but preferably a laser having a wavelength of 750 nm or more, particularly a gallium-containing laser.
Aluminum-arsenic semiconductor laser (oscillation wavelength 830n
A method of recording by forming a recess in the recording layer by irradiation with a laser beam having an oscillation wavelength in the near infrared or infrared region such as m) is suitable. Also, for reading,
It is possible to use the aforementioned laser beam adjusted to have an intensity that does not cause a change in the recording layer. At this time, writing and reading can be performed by lasers having the same wavelength, or lasers having different wavelengths can be performed.

[0102]

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

(Example 1-1) Outer diameter 130 mmφ and inner diameter 15 m formed by injection molding.
On a surface of a transparent polycarbonate (hereinafter abbreviated as PC) substrate having a donut shape of mφ and a thickness of 1.2 mm and having spiral tracking grooves with a width of 0.6 μm and a pitch of 1.6 μm on the surface, The polymethine dye compound No. A solution prepared by dissolving 3 parts by weight of the polymethine dye compound of (1) in 97 parts by weight of diacetone alcohol was applied by a spinner coating method and then dried to 80
A recording layer of 0Å was obtained.

Then, a PC protective substrate having the same shape as the substrate was provided on the recording layer via a spacer having a thickness of 0.3 mm to prepare an optical disc having an air sandwich structure. An ultraviolet curable adhesive was used to bond the substrate and the spacer and the spacer and the protective substrate together.

The transmittance of light having a wavelength of 830 nm in the recording layer of the optical disk thus obtained was measured by a spectrophotometer (trade name: U-
3400; manufactured by Hitachi, Ltd.).
This is the initial transmittance.

Next, this optical disk was mounted on a turntable, this turntable was rotated at 1800 rpm, and a semiconductor laser having an oscillation wavelength of 830 nm was used to form a spot size of 1.5 μmφ and a recording power of 8 mW on the recording layer from the substrate side. Information is written at a recording frequency of 3 MHz and reproduced at a read power of 0.6 mW, and the reproduced waveform is spectrum analyzed (scanning filter, bandwidth 30 KH
z) to measure the C / N ratio. This is the initial C / N ratio.

Next, the information recording section of this optical disk is set to 10
The C / N ratio after repeated reproduction ⁵ times was measured (repetition reproduction stability).

Further, after preparing a new optical disk of Example 1 prepared by the same procedure as described above and recording information under the same recording conditions as described above, the optical disk was recorded at 85 ° C. After being left for 1000 hours, the transmittance of light having a wavelength of 830 nm and the C / N ratio of recorded information of the recording layer were measured by the same method as described above (environmental storage stability).

Further, in order to evaluate the heat resistance of this optical disk, the C obtained by the evaluation of environmental preservation stability was used.
Change rate of the / N ratio with respect to the initial C / N ratio (ΔC / N)
Was calculated according to the following formula. ΔC / N = [(ab) / a] × 100 However, a: initial value of C / N ratio b: C / N when held for 1000 hours under the condition of 85 ° C.
ratio

The results of the above evaluations are shown in Table 2-1.

[0111]

[Table 9]

(Examples 1-2 to 1-9) The polymethine dye compound No. 1 used in Example 1 was used. The compound of (1) was added to No.
(4), (7), (10), (16), (19), (2
4), (30), and (33) were replaced with a recording medium prepared in the same manner as in Example 1, and each of Examples 1-2 to 1-
9 optical disks were prepared.

The optical discs of Examples 1-2 to 1-9 were repeatedly evaluated for reproduction stability and environmental storage stability in the same manner as in Example 1-1. The results are shown in Table 2-2.

[0114]

[Table 10]

(Examples 1-10 to 1-17) Nos. Used in Example 1 The polymethine dye compound of (1) was added to No.
(23), No. (17), No. (11), No.
(101), No. (103), No. (105), N
o. (107) and No. Optical discs were prepared in the same manner as in Example 1 except that the polymethine dye compound of (108) was used, and the optical discs of Examples 1-10 to 1-17 were prepared.

Then, with respect to the optical disks of Examples 1-10 to 1-17, the repeated reproduction stability and the environmental storage stability were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[0117]

[Table 11]

As is clear from Tables 3 and 2-2, the optical recording medium of the present invention has a C / N ratio decrease rate of 1 at high temperature as compared with the conventional optical recording medium. It can be suppressed to / 2 or less.

(Comparative Examples 1-1 to 1-4) In Example 1, the dye compound No. The compound of (1) is No. 4 shown in Table 4-1. (201), (202), (203) and (2
Optical discs were prepared in the same manner as in Example 1-1 except that the optical discs of Comparative Examples 1-1 to 1-4 were used. Then, the repeated reproduction stability and the environmental preservation stability of the optical discs of Comparative Examples 1-1 to 1-4 were evaluated in the same manner as in Example 1-1. The result is the fourth
Table 2 shows.

[0120]

[Table 12]

[0121]

[Table 13]

Example 1-18 Compound No. (2
01) and the polymethine dye compound No. 1 according to the present invention.
Each of (4) and (4) was mixed with diacetone alcohol in a weight ratio of 1: 2 and applied in the same manner as in Example 1-1 to provide an organic thin film recording layer having a dry film thickness of 850Å, and Example 1-1 was used.
8 optical disks were produced.

Example 1-19 In Example 1-18, compound No. (201) as compound No. (202)
An optical disk of Example 11 was manufactured in the same manner as in Example except that the above was changed. The repeated reproduction stability and the environmental preservation stability of the optical discs of Examples 1-18 and 1-19 were evaluated in the same manner as in Example 1-1. The results are shown in Table 5.

(Example 1-20) The compound No.
A solution prepared by mixing 2 parts by weight of the compound of (2) and 1 part by weight of a nitrocellulose resin (Ohler's lacquer, manufactured by Daicel Chemical Industries, Ltd.) with 97 parts by weight of diacetone alcohol was prepared by a spinner coating method. A recording layer having a dry film thickness of 1000Å was formed by coating on a PC substrate prepared in the same manner as in.

With respect to the repeated reproduction stability and the environmental preservation stability of the optical disc prepared in this way, Example 1-
Evaluation was performed in the same manner as in 1.

(Examples 1-21 to 1-23) Compound Nos. Used in the examples. (2) is the compound No. (5),
An optical disc of the example was manufactured in the same manner as in the example 12 except that the steps (15) and (25) were changed.

The repeated reproduction stability and the environmental preservation stability of the optical disc of the above-mentioned example were evaluated by the same method as in Example 1-1.

The results of the above examples are shown in Table 5.

[0129]

[Table 14]

Example 2-1 A rectangular wallet size (length 54 mm, width 85 mm) having a thickness of 0.4 m
m polycarbonate (hereinafter abbreviated as “PC”) substrate by a hot pressing method, width 3 μm, pitch 12 μm, length 8
A 5 mm striped pre-groove was provided, and the polymethine dye compound No. A solution prepared by mixing 3 parts by weight of the compound of (1) with 97 parts by weight of diacetone alcohol was applied by the bar coating method, and then dried to 1000 Å.
The recording layer is formed, and a transparent PC protective substrate with a wallet size of 0.3 mm and a thickness of 0.3 mm is laminated via an acrylic ester-based dry film, and is adhered using a heat roll to form a close contact structure. The optical card of

With respect to the optical card thus obtained, the transmittance of the recording layer was measured using a semiconductor laser beam having a wavelength of 830 nm.

Then, this optical card is mounted on an optical card recording / reproducing apparatus (manufactured by Canon Inc.), and the optical card is driven in the direction along the pre-groove while the oscillation wavelength is 830n.
spot size of 3.0 μm on the organic thin film recording layer from the side of the PC substrate with a thickness of 0.4 mm by using a semiconductor laser of m
φ, recording power is 3.2 mW, information is written on the recording track between the pre-grooves with a recording pulse of 50 μsec, and then the semiconductor laser light whose power is reduced to 0.3 mW is scanned on the recording track on which the information is recorded. Information was reproduced and the contrast ratio of the reproduced signal was measured. The contrast ratio is calculated by the following formula. Contrast ratio (Cont.) = [(AB) / A] where A: signal strength of unrecorded area B: signal strength of recorded area

Next, the optical card on which this information was recorded was left in the environment of 85 ° C. for 1000 hours in the same manner as in Example 1, and thereafter the transmittance of the recording layer and the contrast of the recorded information were measured as described above. The same method was used. Then, in order to evaluate the heat resistance of this optical card, the rate of change (ΔCont.) Of the contrast ratio after the environmental storage stability test with respect to the initial contrast ratio was determined according to the following formula. ΔCont. = [(Cont.) ₀ − (Con
t. ) ₈₅ ] / (Cont.) ₀ However, (Cont.) ₀ : Initial contrast ratio (Cont.) ₈₅ : Contrast ratio after environmental preservation stability test

Also, a new optical card of Example 2-1 prepared by the same procedure as described above is prepared, and this optical card is used as a fade meter (trade name: Xenon Long Life Fade Meter FAL-25AX; Suga Test). The light resistance test was performed for 10 hours using a machine.

(Examples 2-2 to 2-9) In Example 2-1, the compound No. The compound of (1) is replaced with the compound N
o. (7), (15), (33), (2), (4),
Other than changing to (30), (102) and (104),
Optical cards of Examples 2-2 to 2-9 were produced in the same manner as in Example 2-1, and environmental storage stability and light resistance stability were evaluated in the same manner as in Example 2-1.

The results of Examples 2-1 to 2-9 are shown in Table 6.

[0137]

[Table 15]

(Comparative Examples 2-1 to 2-4) In Example 2-1, the dye compound No. The compound of (1) was added to No. 3 shown in Table 3 above. Optical cards were prepared in the same manner as in Example 2-1 except that (201), (202), (203) and (204) were used, and the optical cards of Comparative Examples 2-1 to 2-4 were prepared. . The environmental preservation stability and the light resistance stability of the optical cards of Comparative Examples 2-1 to 2-4 described above were evaluated in Example 2
It evaluated similarly to -1. The results are shown in Table 7.

[0139]

[Table 16]

Example 3-1 A solution was prepared by dissolving 3 parts by weight of the polymethine dye compound used in Example 2-5 in 97 parts by weight of diacetone alcohol.

On the other hand, 200 wallet-sized PC substrates used in Example 2-1 were prepared, and the above solution was continuously applied onto the substrates by a roll coating method to form a dry film on each substrate. A recording layer having a thickness of 1000Å was formed. Then, using each substrate formed with a recording layer, Example 2
200 optical cards were prepared in the same manner as in -1.

The recording layer is applied first,
Optical cards manufactured using the 10th, 50th, 100th, and 200th substrates (hereinafter, optical card No.
1, No. 10, No. 50, No. 100 and No.
200), each of which is mounted on an optical card recording / reproducing device, and the optical card is driven in a direction along the pre-groove, and a semiconductor laser having an oscillation wavelength of 830 nm is used from the PC board side. Information was recorded under the following recording conditions by irradiating the recording layer on the recording track between the grooves. Recording conditions Laser spot size: 3 μmφ Recording power: 3.2 mW Recording pulse: 50 μsec. Card feeding speed: 60 mm / sec.

Then, the semiconductor laser with the power reduced to 0.3 mW is scanned on the recording track on which information is recorded to reproduce the information, and the reproduced waveform is spectrally analyzed to determine the noise of each optical card. The level and C / N ratio were measured, and No. N for the noise level of one optical card
o. 10, No. 50, No. 100 and No. 200
The reduction rate of the noise level of the optical card was evaluated.

The results are shown in Table 7-1.

(Examples 3-2 to 3-5) The above Example 3-
No. 1 in No. 1 The compound of (2) was added to No. (4), (3
Example 3 except that 0), (33) and (101) were used instead.
Make 200 optical cards in the same way as in -1,
In the same manner as in Example 3-1, the optical card No. 1, 10, 5
The noise level and C / N ratio were measured and evaluated for 0, 100, and 200 optical cards. The result is 7-1
Shown in the table.

[0146]

[Table 17]

Comparative Examples 3-1 and 3-2 Example 3-
No. 1 in No. 1 The compound of (2) was added to No. 200 optical cards were prepared in the same manner as in Example 3-1 except that (201) and (202) were used. Noise level and C / N for 1, 10, 50, 100 and 200 optical cards
The ratio was measured and evaluated. The results are shown in Table 7-2.

Reference Example 1 N in the above Example 3-1
o. The compound of (2) was added to No. 200 optical cards were prepared in the same manner as in Example 3-1 except that the optical card No. 3 was changed to that in Example 3-1. 1, 10, 50,
The noise level and C / N ratio were measured and evaluated for 100 and 200 optical cards. The results are shown in Table 7-2.

[0149]

[Table 18]

As is clear from Tables 7-1 and 7-2, the optical card N in Examples 3-1 to 3-5 was used.
o. 1 and No. While the rate of change of the noise level between the optical card N and the signal of 200 is zero, in the comparative example 3-1, the optical card N
o. 1 and No. Noise level between 200 and 6.7%
Also rises, and in Comparative Example 3-2, the noise level is 6.
That's up 6%.

Also in the reference example 1, the noise level is 2.
It rose by 7%. This is because the polymethine dye compound used in Comparative Examples 3-1 and 3-2 and Reference Example 1 does not have sufficient solvent solubility, and is easily caused by a slight change in the concentration of the coating solution that occurs when coated on a plurality of substrates. Precipitation of solid matter such as microcrystals occurred, which is considered to be the cause of noise. On the other hand, the polymethine compounds of the present invention of Examples 3-1 to 3-5 have high solubility in a solvent that does not damage the plastic, and crystals are unlikely to occur even if the concentration changes slightly in the coating step. It is considered that it is possible to stably obtain an optical recording medium having a low noise level because crystals are rarely mixed in.

Example 4-1 As the coating solution for the recording layer in Example 2-1, polymethine dye compound No.
(1) An optical card similar to Example 2-1 except that 2.4 parts by weight and 0.6 parts by weight of a stabilizer represented by the following structural formula were mixed with 97 parts by weight of diacetone alcohol. Was prepared and the initial transmittance and the transmittance after the fade meter light resistance test (100 hours) were performed in the same manner as in Example 2-1. The results are shown in Table 8.

[0153]

[Outside 39]

[0154]

[Table 19]

[0155]

As described above, according to the present invention, it is possible to obtain an optical recording medium having excellent heat resistance and further improved stability under high temperature conditions.

Further, according to the present invention, it is possible to obtain an optical recording medium which is always low in noise level and excellent in heat resistance.

Further, according to the present invention, an optical recording medium excellent in heat resistance can be manufactured with high productivity.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an embodiment of an optical recording medium of the present invention.

FIG. 2 is a schematic cross-sectional view of another embodiment of the optical recording medium of the present invention.

FIG. 3 is a schematic cross-sectional view of another embodiment of the optical recording medium of the present invention.

FIG. 4 is a schematic cross-sectional view of another embodiment of the optical recording medium of the present invention.

[Explanation of symbols]

 1 substrate 2 recording layer 3 protective layer 4 undercoat layer

Claims (15)

[Claims] 1. An optical recording medium having a recording layer containing an organic dye represented by the following general formula (I). [Outer 1] (In the formula, R _{0 to} R ₅ are hydrogen atoms or monovalent organic residues, and at least one of R _{0 to} R ₃ is a monovalent organic residue having a fluorine atom. M is 0, 1 Or 2, [External 2] Indicates an anion residue. ) 2. The monovalent organic residue having a fluorine atom is a substituted or unsubstituted alkyl group having a fluorine atom, a substituted or unsubstituted alkenyl group having a fluorine atom, a substituted or unsubstituted atom having a fluorine atom. 2. The optical recording medium according to claim 1, which is an aralkyl group or a substituted or unsubstituted aryl group having a fluorine atom. 3. The optical recording medium according to claim 2, wherein the monovalent organic residue having a fluorine atom is a substituted or unsubstituted alkyl group containing a fluorine atom. 4. The optical recording medium according to claim 1, wherein in the monovalent organic residue having a fluorine atom, when the number of carbon atoms is n, the number of fluorine atoms is 0.1n or more and 3n or less. 5. The optical recording according to claim 4, wherein in the monovalent organic residue having a fluorine atom, when the number of carbon atoms is n, the number of fluorine atoms is 0.5n or more and 1.8n or less. Medium. 6. At least _one of R ₀ and R ₁ and R
The optical recording medium according to claim 1, wherein at least one of ₂ and R ₃ is a monovalent organic residue having a fluorine atom. 7. The optical recording medium according to claim 6, wherein each of R _{0 to} R ₃ is a monovalent organic residue having a fluorine atom. 8. The light according to claim 1, wherein R ₄ and R ₅ are monovalent organic residues having no fluorine atom, and at least one of R ₄ and R ₅ is a substituted or unsubstituted aryl group. recoding media. 9. The optical recording medium according to claim 1, wherein at least one of R ₄ and R ₅ is an amino-substituted aryl group represented by the following formula (III). [Outside 3] (R ₆ and R ₇ are a hydrogen atom or a monovalent organic residue, and at least one of R ₆ and R ₇ is a methyl group or an ethyl group having a fluorine atom.) 10. An optical recording medium having a recording layer containing a polymethine dye represented by the following general formula (II). [Outside 4] (In formula [outside 5] Represents an anion residue, and R ₀ ′ to R ₃ ′ are R ₀ ′ and R
₁ ′ and at least one combination of R ₂ ′ and R ₃ ′ is N
Together with a substituted or unsubstituted pyrrolidine ring having a fluorine atom, a substituted or unsubstituted piperidine ring having a fluorine atom, a substituted or unsubstituted morpholine ring having a fluorine atom, a substituted or unsubstituted tetrahydropyridine ring having a fluorine atom Or a substituted or unsubstituted cyclohexylamine ring having a fluorine atom represented by the following formula: Represents a group of atoms necessary for forming a hydrogen atom, other represents a hydrogen atom or a monovalent organic residue, and R ₄ ′ and R ₅ ′ represent a hydrogen atom or a monovalent organic residue. m is 0, 1 or 2. ) 11. The R ₄ ′ and R ₅ ′ are monovalent organic residues having no fluorine atom, and at least one of R ₄ ′ and R ₅ ′ is a substituted or unsubstituted aryl group. Item 10. The optical recording medium of item 10. 12. The optical recording medium according to claim 10, wherein at least one of R ₄ ′ and R ₅ ′ is an amino-substituted aryl group represented by the following formula (IV). [Outside 7] (However, R ₆ ′ and R ₇ ′ are hydrogen atoms or monovalent organic residues, and at least one of R ₆ ′ and R ₇ ′ is a methyl group or an ethyl group having a fluorine atom.) 13. The optical recording medium according to claim 10, wherein at least one of R ₄ ′ and R ₅ ′ is an amino-substituted aryl group represented by the following formula (V). [Outside 8] (However, R ₈ ′ and R ₉ ′ are a pyrrolidine ring substituted with a methyl group in which one or more hydrogen atoms are substituted with a fluorine atom together with N in the combination of R ₈ ′ and R ₉ ′, N And a piperidine ring substituted with a methyl group obtained by substituting one or more hydrogen atoms with a fluorine atom, and substituted with a methyl group obtained with one or two or more hydrogen atoms substituted with a fluorine atom together with N Morpholine ring, 1 with N
A tetrahydropyridine ring substituted with one or more hydrogen atoms substituted with a fluorine atom and a methyl group, N
And the group of atoms necessary to form a cyclohexylamine ring substituted with a methyl group in which one or more hydrogen atoms are substituted with fluorine atoms. ) 14. A method for producing an optical recording medium having a recording layer containing an organic dye represented by the following general formula (I), which comprises a coating liquid containing the organic dye represented by the following general formula (I). A method for producing an optical recording medium, which comprises applying the composition onto a substrate to form the recording layer. [Outside 9] (In the formula, R _{0 to} R ₅ are hydrogen atoms or monovalent organic residues, and at least one of R _{0 to} R ₃ is a monovalent organic residue having a fluorine atom. M is 0, 1 Or 2, and Indicates an anion residue. ) 15. A method for producing an optical recording medium having a recording layer containing an organic dye represented by the following general formula (II), comprising a coating liquid containing the organic dye represented by the following general formula (II). A method for producing an optical recording medium, which comprises applying the composition onto a substrate to form the recording layer. [Outside 11] (In the formula [outside 12] Represents an anion residue, and R ₀ ′ to R ₃ ′ are R ₀ ′ and R
₁ ′ and at least one combination of R ₂ ′ and R ₃ ′ is N
Together with a substituted or unsubstituted pyrrolidine ring having a fluorine atom, a substituted or unsubstituted piperidine ring having a fluorine atom, a substituted or unsubstituted morpholine ring having a fluorine atom, a substituted or unsubstituted tetrahydropyridine ring having a fluorine atom Or a substituted or unsubstituted cyclohexylamine ring having a fluorine atom represented by the following formula: Represents a group of atoms necessary for forming a hydrogen atom, other represents a hydrogen atom or a monovalent organic residue, and R ₄ ′ and R ₅ ′ represent a hydrogen atom or a monovalent organic residue. m is 0, 1 or 2. )