JP4516784B2 - Novel oxonol dye compound and optical information recording medium - Google Patents

Description

  The present invention relates to oxonol dyes. Oxonol dyes have long been used as filter dyes for silver halide light-sensitive materials. In recent years, it has been found that the present invention can also be applied to a heat mode type information recording medium in which information can be written (recorded) or read (reproduced) using a laser beam having a high energy density, and research has been actively conducted. In particular, the present invention is an oxonol dye that can be preferably used for a heat mode type information recording medium such as a write once digital versatile disk (DVD-R) suitable for recording information using visible laser light. It is about.

Conventionally, an information recording medium (optical disk) capable of recording information only once by a laser beam is known. The information recording medium is also referred to as a write-once type CD (so-called CD-R), and has an advantage that it can provide a small amount of CD at a reasonable price and quickly compared with the production of a conventional CD. The demand for computers is increasing with the spread of computers. A typical structure of a CD-R type information recording medium is such that a recording layer made of an organic dye, a reflective layer made of a metal such as gold, and a protective layer made of resin are laminated in this order on a transparent disk-shaped substrate. It is.
Information is recorded on the optical disk by irradiating a near-infrared laser beam (usually a laser beam having a wavelength of around 780 nm) to locally generate heat and deform the recording layer. On the other hand, reading (reproduction) of information is usually performed by irradiating a laser beam having the same wavelength as the recording laser beam, and reflecting the portion of the recording layer where heat is deformed (recorded portion) and the portion where the recording layer is not deformed (unrecorded portion). This is done by detecting the difference in rate.

  In recent years, information recording media with higher recording density have been demanded. In order to increase the recording density, it is effective to reduce the diameter of the irradiated laser beam, and it is theoretically known that laser light with a shorter wavelength can be reduced to a smaller value, which is advantageous for higher density. It has been. Accordingly, development of an optical disk for recording / reproducing using a laser beam having a wavelength shorter than 780 nm, which has been conventionally used, has been developed. For example, it is referred to as a recordable digital versatile disk (so-called DVD-R). Optical discs to be sold are on the market. This optical disk has a recording layer made of a dye on a transparent disk-like substrate having a diameter of 120 mm or 80 mm in diameter, on which a pregroove having a track pitch of 0.8 μm narrower than 1.6 μm of CD-R is formed, and usually A structure in which two discs each having a reflective layer and a protective layer further provided on the recording layer, or a disc-like protective substrate having substantially the same dimensions as the disc are bonded with an adhesive with the recording layer inside. It is manufactured to be. The DVD-R is recorded and reproduced by irradiating with visible laser light (usually laser light having a wavelength in the range of 600 nm to 700 nm), and can be recorded at higher density than the CD-R type optical disc. It is said.

  Since the DVD-R type information recording medium can record several times the amount of information as compared with the conventional CD-R type, the DVD-R type information recording medium has not only high recording sensitivity but also a large amount of information. Therefore, it is desirable that the error rate be small even for high-speed recording. In addition, since a recording layer made of a dye generally has low stability over time to heat or light, it is desired to develop a recording layer that can maintain stable performance against heat or light over a long period of time.

Patent Documents 1 to 5 below disclose a heptamethine oxonol dye having a specific structure and an optical recording medium using the same. However, optical recording media using these dyes have insufficient light fastness, solubility when preparing a dye coating liquid, and stability with time of dissolution of the coating liquid. It was also found that the recording sensitivity of the optical recording medium was insufficient.
Japanese Patent Laid-Open No. 2002-249674 JP 2002-52825 A JP 2000-280622 A JP 2000-108520 A JP 2000-52658 A

  The problem to be solved by the invention is to develop a dye having higher recording sensitivity when used in an optical recording medium as compared with a conventionally known dye. Further, it is to develop a dye imparted with high-speed recording suitability, and to develop a dye that reduces jitter during recording and reproduction of an optical recording medium. The development of a dye having high solubility in a coating solution and high stability over time in the coating solution. Another object is to improve the light fastness and wet heat fastness of the optical recording medium.

  As a result of intensive studies by the inventors of the present invention, a dye that solves the above problems and an optical recording medium using the same have been developed.

[1] A compound having a structure represented by the following general formula (I).

In the general formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkoxy, halogen atom or alkoxycarbonyl substituted or unsubstituted alkyl group, alkoxy or halogen atom substituted or unsubstituted aryl group Represents. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom , an unsubstituted alkyl group, an alkoxy or halogen atom substituted or unsubstituted aryl group, a halogen atom , It represents an unsubstituted acyl group , an unsubstituted alkoxy group , an unsubstituted acylamino group, an oxo- substituted or unsubstituted heterocyclic group, or an alkoxy- substituted or unsubstituted aryloxy group. R ^21, R ²² each independently represents an unsubstituted alkyl group or an unsubstituted aryl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represent 0, 1, 2, or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4. When at least one of R ^{23 to} R ³² represents a substituent, the substituent is independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group or silyl group.
[2] A compound having a structure represented by the following general formula (II).

In the general formula, R ^1, R ² each independently represents a hydrogen atom, alkoxy, halogen or alkoxycarbonyl substituted or unsubstituted alkyl group, alkoxy or halogen atom or a substituted or unsubstituted aryl group. R ^c and R ^d each independently represents an unsubstituted alkyl group, which are bonded to form a ring structure. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom , an unsubstituted alkyl group, an alkoxy or halogen atom substituted or unsubstituted aryl group, a halogen atom , It represents an unsubstituted acyl group , an unsubstituted alkoxy group , an unsubstituted acylamino group, an oxo- substituted or unsubstituted heterocyclic group, or an alkoxy- substituted or unsubstituted aryloxy group. L is Ru der divalent linking group.
R ^21, R ²² each independently represents an unsubstituted alkyl group or an unsubstituted aryl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represent 0, 1, 2, or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4. When at least one of R ^{23 to} R ³² represents a substituent, the substituent is independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group or silyl group.
[3] An optical information recording medium comprising a compound having a structure represented by the following general formula (I):

In the general formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom , alkoxy, halogen atom or alkoxycarbonyl substituted or unsubstituted alkyl group, alkoxy or halogen atom substituted or unsubstituted aryl group Represents. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom , an unsubstituted alkyl group, an alkoxy or halogen atom substituted or unsubstituted aryl group, a halogen atom , It represents an unsubstituted acyl group , an unsubstituted alkoxy group , an unsubstituted acylamino group, an oxo- substituted or unsubstituted heterocyclic group, or an alkoxy- substituted or unsubstituted aryloxy group. R ^21, R ²² each independently represents an unsubstituted alkyl group or an unsubstituted aryl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represent 0, 1, 2, or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4. When at least one of R ^{23 to} R ³² represents a substituent, the substituent is independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group or silyl group.
In addition, the compound having the structure represented by the general formula (I) may be hereinafter referred to as “a compound represented by the general formula (I)” or “a dye compound represented by the general formula (I)”. In addition, the compound having the structure represented by the general formula (II) may hereinafter be referred to as “a compound represented by the general formula (II)” or “a dye compound represented by the general formula (II)”. .

  The dye of the invention, when used in an optical recording medium, has features such as higher recording sensitivity, higher recording performance, and lower jitter during recording / reproduction of the optical recording medium when compared to conventionally known dyes. In addition, the light fastness and wet heat fastness of the optical recording medium are improved. Furthermore, the solubility in the coating solution is high, and the dissolution stability with the coating solution is high and excellent.

The present invention is described in detail below.
In general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Preferably, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, 2-methoxyethyl, 2-chloroethyl, 2-ethoxycarbonylethyl), a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, phenyl group, p-methoxyphenyl group, m-chlorophenyl group, o-fluoropheno) Group, naphthyl group).
R ¹ , R ² , R ³ and R ⁴ are more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. R ¹ and R ³ are the same, and R ² and R ⁴ are preferably the same. For example, (R ¹ / R ² ) = (R ³ / R ⁴ ) = (methyl / n-propyl), (ethyl / n-propyl), (methyl / ethyl), (methyl / i-propyl), etc. . Here, (R ¹ / R ² ) = (R ³ / R ⁴ ) = (methyl / n-propyl) means that R ¹ , R ³ are methyl groups, and R ² and R ⁴ are n-propyl groups. To express.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (for example, methyl, Ethyl, n-propyl, t-butyl, n-hexyl), substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, phenol, p-methoxyphenyl, m-chlorophenol, o-chlorophenol, naphthyl), halogen Atom (for example, chlorine atom, bromine atom, iodine atom), substituted or unsubstituted acyl group having 2 to 12 carbon atoms (for example, acetyl, pivaloyl, benzoyl), substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms (For example, methoxy, ethoxy, n-propoxy, n-octyl), a substituted or unsubstituted acylamino group having 1 to 10 carbon atoms (for example, acetylamino, Valoylamino), a substituted or unsubstituted heterocyclic group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms (for example, phenoxy, p-methoxyphenoxy). R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are all preferably hydrogen atoms. R ⁹ is preferably a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Most preferably, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are all hydrogen atoms.
R ²¹ and R ²² are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted carbon group having 1 to 4 carbon atoms. Represents a heterocyclic group. R ²¹ and R ²² are preferably an aryl group having 6 to 12 carbon atoms (preferably a phenyl group or a naphthyl group). R ²¹ and R ²² are preferably the same.
R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. Substituents are halogen atoms, alkyl groups (including cycloalkyl groups and bicycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups , Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Famoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphine group Examples include a finyloxy group, a phosphinylamino group, and a silyl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ are preferably all hydrogen atoms.
R ³¹ and R ³² each independently represents a substituent. Examples of the substituent include those described for R ^{23 to} R ³⁰ above. R ³¹ and R ³² are preferably a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a halogen atom, or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms.
s and t each independently represent 0, 1, 2, or 3. Both s and t are preferably 0.
n and m each independently represent 1 or 2. n and m are both preferably 1.
The maximum value of s + n is 4, and the maximum value of t + m is 4.

In the structure represented by the general formula (I), R ¹ , R ² , R ³ and R ⁴ are preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are all hydrogen atoms, and R ²¹ and R ²² are both an aryl group having 6 to 12 carbon atoms (preferably a phenyl group or a naphthyl group, more preferably a phenyl group). R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , and R ³⁰ are all hydrogen atoms, and R ³¹ and R ³² are substituted or unsubstituted carbon atoms. 1 to 10 alkoxy groups, halogen atoms, substituted or unsubstituted acyl groups having 2 to 10 carbon atoms, s and t are both 0 and 1 (preferably 0), and n and m are both 1.

The dye of the present invention can also form a dimer in which two molecules are covalently bonded. In this case, exemplary manner in which the R ³ and / or R ⁴ is bonded to R ³ and / or R ⁴ and the other dye of one dye.
A preferable structure of the dimer is a structure represented by the general formula (II).
In the general formula (II), in the general formula, R ¹ , R ² , R ^c and R ^d each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, substituted or It represents an unsubstituted acyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryloxy group. L is a divalent linking group, and R ^c and R ^d may be bonded to form a ring structure.
R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represent 0, 1, 2, or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4.
Wherein ^{(II), R 1, R} 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 21, R 22, R 23, R 24 , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , s, t, n, m are the preferred examples described for the corresponding substituents of general formula (I). Likewise preferred. L is preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. R ^c and R ^d are preferably the same as described for R ¹ .
R ^c and R ^d are preferably bonded to each other and form a ring structure with L. Among them, those that form a cycloalkyl structure are preferable. Furthermore, what forms a 5-membered or 6-membered ring (preferably 6-membered ring) is preferable.

  The dye represented by the general formula (I) of the present invention is a novel compound. These dyes were synthesized for the first time by the inventors' research.

  Although the preferable specific example of the compound represented by general formula (I) and general formula (II) of this invention is given to the following, this invention is not limited to these.

  A general oxonol dye part can be synthesized by a condensation reaction between a corresponding active methylene compound and a methine source (a compound used for introducing a methine group into a methine dye). Details of this type of compound are described in JP-B-39-22069, JP-A-43-3504, JP-A-52-38056, JP-A-54-38129, JP-A-55-10059, JP-A-58-35544, JP-A-49-49. -99620, 52-92716, 59-16834, 63-316853, 64-40827, and British Patent Nos. 1339986, U.S. Pat. Nos. 3,247,127, 4042397, and 4181225. Nos. 5213956 and 5260179 can be referred to.

The synthesis of the dye compound represented by the general formula (I) of the present invention will be described. For example, those in which R ¹ = R ³ and R ² = R ⁴ can be synthesized according to the following scheme.

In the formula, R ^{1 to} R ¹¹ , R ^{21 to} R ³² , n, m, s, and t are the same as those defined in the general formula (I). Ra and Rb each independently represent a substituent, and u and v are each independently 0 to 5.
For example, those in which R ¹ ≠ R ³ and R ² ≠ R ⁴ can be synthesized according to the following scheme.

In the formula, R ^{1 to} R ¹¹ , R ^{21 to} R ³² , n, m, s, and t are the same as those defined in the general formula (I). Ra and Rb each independently represent a substituent, and u and v are each independently 0 to 5.

  The compound represented by the general formula (II) of the bis type can be synthesized according to the following scheme.

In the formula, R ^{1 to} R ¹¹ , R ^{21 to} R ³² , n, m, s, and t are the same as those defined in the general formula (I). Ra and Rb each independently represent a substituent, and u and v are each independently an integer of 0 to 5. L is a divalent linking group, and R ^c and R ^d are independently the same as R ¹ . R ^c and R ^d may combine to form a ring structure.

  The dye compound represented by the above general formula (I) according to the present invention may be used alone or in combination of two or more. Moreover, you may use together the pigment compound concerning this invention, and the pigment compound other than this.

The information recording medium of the present invention is not particularly limited as long as it has the dye compound represented by the general formula (I) as a recording layer, but the optical information recording medium of the present invention is applied to a CD-R. The dye compound represented by the above general formula (I) is formed on a transparent disk-shaped substrate having a thickness of 1.2 ± 0.2 mm on which pregrooves having a track pitch of 1.4 to 1.8 μm are formed. The recording layer, the light reflecting layer, and the protective layer are preferably included in this order. Moreover, when applying to DVD-R, it is preferable that it is the following two aspects.

(1) On a transparent disk-shaped substrate having a thickness of 0.6 ± 0.1 mm on which pregrooves having a track pitch of 0.6 to 0.9 μm are formed, the dye compound represented by the above general formula (I) An optical information recording medium in which two laminates each including a recording layer and a light reflecting layer are joined so that the recording layers are on the inside, and the thickness is 1.2 ± 0.2 mm. .

(2) A dye compound represented by the above general formula (I) is formed on a transparent disk-shaped substrate having a thickness of 0.6 ± 0.1 mm on which pregrooves having a track pitch of 0.6 to 0.9 μm are formed. A laminated body provided with a recording layer and a light reflecting layer, and a transparent disk-shaped protective substrate having the same shape as the disk-shaped substrate of the laminated body are bonded so that the recording layer is inside, and the thickness is 1 An optical information recording medium configured to be 2 ± 0.2 mm. In the DVD-R type optical information recording medium, a protective layer may be further provided on the light reflecting layer.

  The information recording medium of the present invention can be manufactured, for example, by the method described below. The substrate (including the protective substrate) can be arbitrarily selected from various materials used as a substrate of a conventional information recording medium. Examples of the substrate material include glass; polycarbonate; acrylic resin such as polymethyl methacrylate; vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer; epoxy resin; amorphous polyolefin and polyester; You may use them together. These materials can be used as a film or as a rigid substrate. Among the above materials, polycarbonate is preferable from the viewpoint of moisture resistance, dimensional stability, price, and the like.

  An undercoat layer may be provided on the surface of the substrate on which the recording layer is provided for the purpose of improving the flatness, improving the adhesive force, and preventing the recording layer from being altered. Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfonated. High molecular substances such as polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; and silane coupling agents And the like. The undercoat layer is formed by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying this coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. can do.

  On the substrate (or undercoat layer), irregularities (pregrooves) representing information such as tracking grooves or address signals are formed. The pregroove is preferably formed directly on the substrate at the track pitch when a resin material such as polycarbonate is injection molded or extruded. Further, the pregroove may be formed by providing a pregroove layer. As a material of the pregroove layer, a mixture of at least one monomer (or oligomer) of monoester, diester, triester and tetraester of acrylic acid and a photopolymerization initiator can be used. For example, the pregroove layer is formed by, first, applying a liquid mixture comprising the above acrylate ester and a polymerization initiator on a precisely formed master (stamper), and further placing a substrate on the coating liquid layer. After that, the coating layer is cured by irradiating ultraviolet rays through the substrate or the mother die, and the substrate and the coating layer are fixed. Subsequently, it can obtain by peeling a board | substrate from a mother mold.

On the surface of the substrate (or undercoat layer) on which the pregroove is formed, a recording layer containing the dye of claim 1, preferably the dye compound represented by the general formula (I) according to the present invention. Is provided.
The recording layer can further contain various anti-fading agents for improving light resistance. Representative examples of the anti-fading agent include metal complexes, diimmonium salts, aminium salts represented by general formula (III), (IV) or (V) described in JP-A-3-224793, and JP-A-2-300287. And nitroso compounds disclosed in JP-A-2-300288 and TCNQ derivatives disclosed in JP-A-10-151861.

  The recording layer is formed by dissolving the dye according to the present invention (the compound represented by the general formula (I) or (II), if necessary, other combined dye), and further, if desired, a quencher, a binder and the like in a solvent. It can be carried out by preparing a coating solution and then applying the coating solution to the substrate surface to form a coating film and then drying. Examples of the solvent for the coating solution for forming the dye recording layer include esters such as butyl acetate, ethyl lactate, and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; chlorinated carbonization such as dichloromethane, 1,2-dichloroethane, and chloroform. Hydrogen; Amides such as dimethylformamide; Hydrocarbons such as cyclohexane; Ethers such as tetrahydrofuran, ethyl ether and dioxane; Alcohols such as ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol; 2,2,3 Fluorine solvents such as 1,3-tetrafluoropropanol; glycosyl such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether And the like ethers. The said solvent can be used individually or in combination of 2 or more types in consideration of the solubility of the compound to be used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution depending on the purpose.

  Examples of binders include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin, rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene, polyisobutylene; polyvinyl chloride, polyvinylidene chloride, Vinyl resins such as polyvinyl chloride and polyvinyl acetate copolymers; Acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Polyvinyl alcohol, chlorinated polyethylene, epoxy resins, butyral resins, rubber derivatives, phenol-formaldehyde resins And a synthetic organic polymer such as an initial condensate of a thermosetting resin. When a binder is used in combination as a material for the recording layer, the amount of the binder used is generally in the range of 0.01 to 50 times (mass ratio), preferably 0.1 to 5 times the amount of the dye. It is in the range of (mass ratio). The pigment concentration of the coating solution thus prepared is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.

  Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range of 20 to 500 nm, preferably in the range of 50 to 300 nm.

  A reflective layer is provided on the recording layer for the purpose of improving reflectivity during information reproduction. The light-reflective substance that is the material of the reflective layer is a substance having a high reflectivity with respect to laser light. Examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. , Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi And metals such as semimetals and stainless steels. Of these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable, and Ag is particularly preferable. These substances may be used alone or in combination of two or more or as an alloy. The reflective layer can be formed on the recording layer, for example, by vapor deposition, sputtering or ion plating of the reflective material. The thickness of the reflective layer is generally in the range of 10 to 300 nm, preferably in the range of 50 to 200 nm.

A protective layer may be provided on the reflective layer for the purpose of physically and chemically protecting the recording layer and the like. This protective layer may be provided on the side where the base recording layer is not provided for the purpose of improving scratch resistance and moisture resistance. Examples of the material used for the protective layer include inorganic substances such as SiO, SiO ₂ , MgF ₂ , SnO ₂ , and Si ₃ N _4, and organic substances such as thermoplastic resins, thermosetting resins, and UV curable resins. be able to. The protective layer can be formed, for example, by laminating an adhesive layer on the reflective layer and / or the substrate with a film obtained by plastic extrusion. Or you may provide by methods, such as vacuum evaporation, sputtering, and application | coating. In the case of a thermoplastic resin or a thermosetting resin, it can also be formed by preparing a coating solution by dissolving it in an appropriate solvent and then applying and drying the coating solution. In the case of a UV curable resin, it can also be formed by preparing a coating solution as it is or by dissolving it in a suitable solvent, coating the coating solution, and curing it by irradiating with UV light. In these coating liquids, various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added according to the purpose. The thickness of the protective layer is generally in the range of 0.1 to 100 μm. Through the above steps, a laminate in which a recording layer, a reflective layer, and a protective layer as desired can be formed on a substrate can be produced. A two-layered laminate is produced as described above, and these are bonded together with an adhesive so that each recording layer is on the inside, thereby producing a DVD-R type information recording medium having two recording layers. Can be manufactured. Further, a DVD having a recording layer only on one side is obtained by adhering the obtained laminate and a disk-shaped protective substrate having substantially the same dimensions as the substrate of the laminate so that the recording layer is inside. -R type information recording medium can be manufactured.

  The information recording method of the present invention is performed, for example, as follows using the above information recording medium. First, a laser beam for recording such as a semiconductor laser beam is irradiated from the substrate side while rotating the information recording medium at a constant linear velocity or a constant angular velocity. This light irradiation forms a cavity at the interface between the recording layer and the reflective layer (the formation of the cavity is accompanied by deformation of the recording layer or the reflective layer, or deformation of both layers), or the substrate is thin. It is considered that information is recorded when the refractive index is changed due to the deformation of the recording layer or due to discoloration, change in association state, or the like. As the recording light, a semiconductor laser beam having an oscillation wavelength in the range of 770 to 790 nm for the CD-R type and 600 nm to 700 nm (preferably 620 to 680 nm, more preferably 630 to 660 nm) as the DVD-R type is used. . Reproduction of information recorded as described above is performed by irradiating a semiconductor laser beam having the same wavelength as that during recording from the substrate side while rotating the information recording medium at the same constant linear velocity as above and detecting the reflected light. This can be done.

  In a preferred embodiment, the dye of the present invention is used by mixing with a dye having a shorter absorption maximum wavelength than the dye of the present invention. In particular, it is preferably used as a write-once DVD-R dye.

[Example]
The present invention will be described in more detail with reference to examples.

Synthesis of Compound 1 Compound 1 was synthesized according to the following scheme.

(Process 1)
While stirring ice-cooled dimethylformamide 89 ml and methanol 7.4 g, 70.5 g (460 mmol) of phosphorus oxychloride was added. Thereafter, 25 ml (230 mmol) of 2,4-hexadienal was added dropwise at 70 ° C. After reacting at 80 ° C. for 4 hours, the mixture was cooled to room temperature. The reaction solution was added to 600 ml of ice water in which 28.2 g (230 mmol) of sodium perchlorate was dissolved, extracted with 600 ml of methylene chloride, and the organic layer was washed with saturated brine. After drying with magnesium sulfate, 42 ml (460 mmol) of aniline was added and reacted at 25 ° C. for 10 hours. The precipitated crystals were collected by filtration to obtain 44.2 g of intermediate A (161 mmol, 70%).
(Process 2)
Under a nitrogen stream, 50 g (480 mmol) of malonic acid, 68.7 g (673 mmol) of acetic anhydride, and 2 ml of concentrated sulfuric acid were stirred, ice-cooled, and 41.4 g (480 mmol) of 2-pentanone was added dropwise while maintaining the internal temperature at 5 °. . After reacting for 2 hours as it was, extraction was performed by adding 200 ml of ethyl acetate and 200 ml of 10% brine. The organic layer was further washed twice with 10% brine, and then the solvent was distilled off under reduced pressure with an evaporator to obtain Intermediate B in 49.6 g (288 mmol, yield 60%).
(Process 3)
Intermediate B 20.8 g (120 mmol) and dimethylformamide 400 ml were stirred at −10 ° C., and 33.5 ml (240 mol) of triethylamine was added. After maintaining the temperature at −5 ° or less and slowly adding 15.78 g (57 mmol) of Intermediate A for 3 hours, 77.36 g (240 mmol) of tetrabutylammonium bromide was dissolved in 100 ml of methanol and then added, and 200 ml of ethyl acetate, Extraction was performed by adding 200 ml of water. The extract was washed with saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure using an evaporator. Purification was performed using silica gel column chromatography to obtain 34.2 g (50.8 mmol, yield 88.7%) of intermediate C.
(Process 4)
Intermediate D 5.65 g (10 mmol) and methanol 1000 ml were stirred and completely dissolved at 25 ° C., and then intermediate C 11.0 g (16 mmol) dissolved in methanol 50 ml was added dropwise. After stirring at 25 ° C. for 30 minutes, the reaction solution was poured into 1500 ml of water. The precipitated crystals were collected by filtration and dried to obtain 8.53 g (6.28 mmol, yield 78.5%) of Compound 1. The structure of Compound 1 was confirmed by 1HNMR.
[1] Dilute solution absorption spectrum The absorption spectrum of the tetrafluoropropanol solution was measured.
Absorption maximum wavelength: 642 nm
[2] Absorption spectrum absorption maximum wavelength in dye amorphous film: 673 nm

Other dyes of the present invention can be easily synthesized according to the above synthesis examples.
Next, the test result of the light fastness in the amorphous film | membrane of a pigment | dye is shown.

A 1.0 w% tetrafluoropropanol solution of the dyes shown in the table below was prepared as a coating solution. Using a spin coater, coating was performed on a glass substrate and dried to prepare a dye amorphous film. The light fastness test was conducted using a 100,000 lux merry-go-round type xenon fading tester. The dye residual ratio was determined from the ratio between the transmission optical density before irradiation with xenon light and the effect density after irradiation.
The dye coating solution was found to be excellent in both solubility and dissolution stability at the time of preparation. Furthermore, a uniform planar dye film could be prepared during spin coating.

  From Table 1, it can be seen that the compound of the present invention exhibits a high dye residual ratio and excellent light fastness as compared with the comparative compound. In addition, C-26 was used for the cation of the comparative compound d.

Claims (3)

A compound having a structure represented by the following general formula (I).

In the general formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkoxy, halogen atom or alkoxycarbonyl substituted or unsubstituted alkyl group, alkoxy or halogen atom substituted or unsubstituted aryl group Represents. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom , an unsubstituted alkyl group, an alkoxy or halogen atom substituted or unsubstituted aryl group, a halogen atom , It represents an unsubstituted acyl group , an unsubstituted alkoxy group , an unsubstituted acylamino group, an oxo- substituted or unsubstituted heterocyclic group, or an alkoxy- substituted or unsubstituted aryloxy group. R ^21, R ²² each independently represents an unsubstituted alkyl group or an unsubstituted aryl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represents 0, 1, 2 or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4. When at least one of R ^{23 to} R ³² represents a substituent, the substituent is independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group or silyl group. A compound having a structure represented by the following general formula (II).

In the general formula, R ^1, R ² each independently represents a hydrogen atom, alkoxy, halogen or alkoxycarbonyl substituted or unsubstituted alkyl group, alkoxy or halogen atom or a substituted or unsubstituted aryl group. R ^c and R ^d each independently represents an unsubstituted alkyl group, which are bonded to form a ring structure. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom , an unsubstituted alkyl group, an alkoxy or halogen atom substituted or unsubstituted aryl group, a halogen atom , It represents an unsubstituted acyl group , an unsubstituted alkoxy group , an unsubstituted acylamino group, an oxo- substituted or unsubstituted heterocyclic group, or an alkoxy- substituted or unsubstituted aryloxy group. L is Ru der divalent linking group.
R ^21, R ²² each independently represents an unsubstituted alkyl group or an unsubstituted aryl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represent 0, 1, 2, or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4. When at least one of R ^{23 to} R ³² represents a substituent, the substituent is independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group or silyl group. An optical information recording medium comprising a compound having a structure represented by the following general formula (I):

In the general formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom , alkoxy, halogen atom or alkoxycarbonyl substituted or unsubstituted alkyl group, alkoxy or halogen atom substituted or unsubstituted aryl group Represents. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom , an unsubstituted alkyl group, an alkoxy or halogen atom substituted or unsubstituted aryl group, a halogen atom , It represents an unsubstituted acyl group , an unsubstituted alkoxy group , an unsubstituted acylamino group, an oxo- substituted or unsubstituted heterocyclic group, or an alkoxy- substituted or unsubstituted aryloxy group. R ^21, R ²² each independently represents an unsubstituted alkyl group or an unsubstituted aryl group. R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ each independently represents a hydrogen atom or a substituent. R ³¹ and R ³² each independently represents a substituent. s and t each independently represent 0, 1, 2, or 3. n and m each independently represent 1 or 2. The maximum value of s + n is 4, and the maximum value of t + m is 4. When at least one of R ^{23 to} R ³² represents a substituent, the substituent is independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group or silyl group.