KR20040047648A - Optical information recording medium and new oxonol compound - Google Patents

Abstract

PURPOSE: An optical information recording medium and new oxonol compounds are provided to provide a pigment having a big substantial portion of a complex refractive index and an identical or small imaginary portion in comparison with a low-speed recording comparative pigment, thereby realizing an excellent recording feature. CONSTITUTION: While maintaining a good recording feature in a low-speed recording mode, a high reflectivity and a high degree of modulation are realized in a high-speed recording mode. A pigment for an optical information recording medium has a big substantial portion(n) of a complex refractive index and an identical or small imaginary portion(k). More than two chromofores are disposed within a molecule, while the chromofores are combined in the pigment.

Description

Optical information recording medium and new oxonol compound {OPTICAL INFORMATION RECORDING MEDIUM AND NEW OXONOL COMPOUND}

The present invention relates to a heat mode type information recording medium and an information recording method capable of recording or reproducing information by using a high energy density laser light. In particular, the present invention relates to an information recording medium of a hit mode type, such as a recordable digital versatile disc (DVD-R) suitable for recording information using visible laser light.

Background Art Conventionally, an information recording medium (optical disk) capable of recording only one time of information by laser light is known. The information recording medium is also referred to as a recordable CD (so-called CD-R), and has the advantage of providing a small amount of CDs quickly and at a reasonable price, compared to the production of conventional CDs. Therefore, the demand is also increasing. A typical structure of an information recording medium of the CD-R type is a lamination of 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 on a transparent disc-shaped substrate in this order.

The recording of the information onto the optical disc is performed by irradiating laser light in the near infrared region (normally, laser light having a wavelength near 780 nm) by locally exothermic deformation of the recording layer. On the other hand, the information is reproduced by irradiating a laser beam having the same wavelength as the recording laser beam and detecting the difference in reflectance between the portion where the recording layer is deformed (recording portion) and the portion that is not deformed (unrecorded portion).

In recent years, information recording media having higher recording densities have been demanded. In order to increase the recording density, it is effective to collect the light diameter of the irradiated laser smaller, and the laser light with shorter wavelength can be collected smaller. Therefore, it is theoretically known that it is advantageous to increase the density. Accordingly, development of an optical disc for recording and reproducing using a laser light having a shorter wavelength than 780 nm, which is conventionally used, has been proposed. For example, an optical disc called recordable digital video disc (so-called DVD-R) is proposed. It is. This optical disk has a recording layer made of a pigment on a transparent disk substrate having a diameter of 120 mm or a diameter of 80 mm, with a track pitch of 0.8 µm pre-groove narrower than 1.6 µm of CD-R, and usually The disk is manufactured so as to have a structure in which two disks formed by further forming a reflective layer and a protective layer on the recording layer, or a disk-shaped protective substrate of approximately the same size as the disk, are bonded with an adhesive with the recording layer inward. The DVD-R records and reproduces light by irradiating visible laser light (normally, laser light having a wavelength in the range of 600 nm to 700 nm) to enable recording of higher density than that of a CD-R type optical disk.

Since the DVD-R type information recording medium can record several times the amount of information compared to the conventional CD-R type, not only has a high recording sensitivity, but also because of the necessity of quickly processing a large amount of information. It is desirable to have a low occurrence rate of errors even for high-speed recording. Moreover, since the recording layer which consists of dyes generally has low stability with respect to heat or light over time, development of the recording layer which can maintain stable performance also with respect to heat or light over a long period of time is desired.

Japanese Patent Laid-Open No. 10-226170 [Patent Document 1] discloses a DVD-R type information recording medium having a recording layer made of a cyanine dye formed on a substrate. By using this dye compound, an information recording medium having high recording sensitivity and high reflectance is obtained. Japanese Patent Laid-Open No. 2001-287456 [Patent Document 2] discloses an information recording medium on which a recording layer made of a cyanine dye compound is formed on a substrate. It is possible to keep the recording characteristics stable over time. On the other hand, Japanese Patent Laid-Open No. 63-209995 [Patent Document 3] discloses a CD-R type information recording medium having a recording layer made of an oxonol dye on a substrate. By using this dye compound, stable recording and reproducing characteristics can be maintained for a long time. And here, there is described an oxonol pigment compound in which ammonium is introduced into the molecule in the form of a salt. In addition, Japanese Patent Laid-Open No. 2000-52658 [Patent Document 4] describes an oxonol dye compound which exhibits high light resistance and durability and provides an optical information recording medium having good recording characteristics.

The inventor of the present invention uses various cyanine pigment compounds and oxonol pigment compounds described in the above publication in a DVD-R type optical information recording medium, and examined the performance thereof. As a result, the DVD-R type optical information recording medium containing the dye compound in the recording layer exhibits very good recording characteristics in the low speed recording at the same speed and about 2 times the speed, while being relatively fast at 4x or higher speed. Although it showed excellent recording characteristics, it turned out that it does not reach practically enough performance in modulation degree and a reflectance. In order to obtain an optical information recording medium that satisfies good recording performance, particularly sufficient reflectance and modulation degree, even in high speed recording of 4 times or more while maintaining good recording characteristics in low speed recording of about 1 to 2 times speed, In the characteristic, the actual portion n of the complex refractive index n + ik is larger than that of the low speed recording dye, and the dummy part k may be a dye having the same or smaller value as that of the low speed recording dye. By the way, it was very difficult to obtain the pigment | dye which has the large part n of complex refractive index, and the same part or small value of the imaginary part k, while maintaining the favorable recording characteristic of low-speed gasoline. SUMMARY OF THE INVENTION An object of the present invention is to realize a large complex portion n of complex refractive indices which realizes high reflectance and high modulation even in high-speed recording of 4x or higher speed while maintaining good recording characteristics in low-speed recording of about 1 to 2x speed. (k) is to provide the same or small pigment. In addition, a dye which achieves sufficiently low jitter at a wide recording speed of 1 to 8 times recording speed is provided.

As a result of the intensive examination by the inventor of this invention, it discovered that the pigment | dye which shows such a predetermined optical characteristic is obtained by the following means.

(1) An optical information recording medium having two or more chromophores in a molecule and containing dyes (preferably in the recording layer) in which the chromophores are bonded without interposing a conjugated bond. The optical information recording medium is preferably a heat mode type optical information recording medium having a recording layer on the substrate capable of recording information by irradiation of laser light.

(2) Pigment on the surface of said pregroove formed side of a transparent disk substrate having a diameter of 120 ± 3 mm or a diameter of 80 ± 3 mm and having a thickness of 0.6 ± 0.1 mm and having a track pitch of 0.6 to 0.9 µm. The heat mode type information recording medium according to (1), or the track pitch 0.6, in which a thickness of 1.2 ± 0.2 mm is obtained by joining two stacks in which a recording layer containing a film is formed so that each recording layer is inward. A recording layer containing a pigment is formed on the surface of the pregroove formed side of a transparent disk-shaped substrate having a diameter of 120 ± 3 mm or 80 ± 3 mm and having a thickness of 0.6 ± 0.1 mm, formed of a pregroove of ˜0.9 μm. The heat mode type information recording medium according to (1), wherein the laminated body and the disc shaped protective plate are bonded to each other so that the recording layer is inward.

(3) The optical information recording medium according to (1) or (2), wherein the dye according to (1) has a structure represented by the following general formula (1).

General formula (1)

[Dye ¹¹ , Dye ¹² , Dye ^2k each independently represents a pigment residue having a chromophore, L ¹¹ , L ^2k each independently does not form a π conjugated system between the chromophores to which they are bonded N represents an integer of 0 to 10, k represents all integers greater than or equal to 0 and less than n, Q represents ions that neutralize the charge, and y represents the number necessary to neutralize the charge.]

(4) The chromophore which forms the pigment residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k of the general formula (1) is at least one of cyanine dye, merocyanine dye and oxonol dye (3) The optical information recording medium described in.

(5) The optical information recording according to (3) or (4), wherein all of the chromophores that form the dye residues represented by Dye ¹¹ , Dye ¹² , and Dye ^2k in the general formula (1) are oxonol dyes. media.

(6) The optical information recording medium according to any one of (1) to (5), which contains a dye having a structure represented by the following general formula (6).

General formula (6)

[In formula, Za <^21> , Za <^22> , Za <^23> , Za <^24> is the atomic group which forms an acidic nucleus each independently, Ma <^21> , Ma <^22> , Ma <^23> , Ma <^24> , Ma <^25> , Ma <^26> are each independently It is a substituted or unsubstituted methine group. L ¹¹ is a divalent linking group that does not form a π conjugate system with two bonds. Ka ²¹ and Ka ²² each independently represent an integer of 0 to 3, respectively. Q represents a monovalent cation that neutralizes charge. Or 2Q to represent a divalent cation. When Ka ²¹ and Ka ²² are 2 or 3, plural Ma ²¹ , Ma ²² , Ma ²⁵ , and Ma ²⁶ may be the same or different.]

(7) An oxonol compound represented by the following general formula (2).

General formula (2)

[Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, and R ²¹ , R ²² , R ³ are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heterocyclic groups , Halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted carbamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted Or an unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted carbamoylamino group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, Of the ring, or unsubstituted alkylsulfinyl group, substituted or unsubstituted aryl sulfinyl group and a substituted or unsubstituted sulfamoyl group represents any. m represents an integer of 0 or more, and when m is 2 or more, some R <^3> may be same or different. Z ^{x +} represents a cation and x represents an integer of 1 or more.]

(8) The optical information recording medium according to any one of (1) to (6), wherein the dye is an oxonol compound represented by the general formula (2) described in (7).

(9) An information recording method, wherein information is recorded by irradiating a laser light having a wavelength of 600 to 700 nm to the optical information recording medium according to any one of (1) to (6) and (8).

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail. In addition, in this invention, when a specific part is called "group", unless it mentions specially, it means that it is not necessarily substituted even if it is substituted by 1 or more types (a maximum number of possible) substituents. For example, an "alkyl group" means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in this invention may be any substituent, whether or not there is substitution. In addition, when specific part is called "ring" in this invention, or when "ring" is contained in "group", unless otherwise indicated, it may be monocyclic, may be condensed, and may be substituted or it may not be substituted. . For example, an "aryl group" may be a phenyl group, a naphthyl group, or a substituted phenyl group.

In General formula (1), Dye ¹¹ , Dye ¹² , and Dye ^2k each independently represent the pigment | dye residue which has chromophore. The chromophore which forms the pigment residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k may be any, but for example, cyanine pigment, styryl pigment, merocyanine pigment, phthalocyanine pigment, oxonol pigment, azo pigment And azamethine pigments, squaria pigments, and metal chelate complex dyes. As a chromophore which forms the pigment | dye residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k , Cyanine pigment | dye, merocyanine pigment | dye, an oxonoline pigment | dye, a phthalocyanine pigment | dye, or a metal chelate pigment | dye is preferable. As a chromophore which forms the pigment | dye residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k , More preferably, it is any of cyanine pigment | dye, merocyanine pigment | dye, and oxonol pigment | dye, and cyanine pigment | dye or oxonol pigment is the most preferable. Do. Although the chromophore which forms the pigment | dye residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k may mutually differ, it may be the same, but the same thing is preferable.

When the chromophore which forms the pigment | dye residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k is a cyanine pigment | dye, the cyanine pigment | dye represented by following General formula (3) is preferable.

General formula (3)

In the formulas, Za ¹ and Za ² each represent an atomic group forming a 5- or 6-membered nitrogen-containing heterocycle, and these also represent a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring, and the like. It may be condensed.

Ra ¹ and Ra ² each represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl, carboxymethyl, 5-carboxypentyl), substituted or unsubstituted alkenyl groups (preferably having 2 to 20 carbon atoms, For example vinyl, allyl), substituted or unsubstituted aryl groups (preferably having 6 to 20 carbon atoms, for example phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), In a substituted or unsubstituted heterocyclic group (preferably having 1 to 20 carbon atoms, for example pyridyl, thienyl, prill, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino) Either one, preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted sulfoalkyl group, More preferably, either a substituted or unsubstituted alkyl group or a substituted or unsubstituted sulfoalkyl group is shown.

Ma ^{1 to} Ma ⁷ each independently represent a methine group and may have a substituent, and as a substituent, for example, an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, i-propyl), a halogen atom ( For example, chlorine, bromine, iodine, fluorine), nitro groups, alkoxy groups having 1 to 20 carbon atoms (eg methoxy, ethoxy), aryl groups having 6 to 26 carbon atoms (eg phenyl, 2- Naphthyl), C0-20 heterocyclic group (for example, 2-pyridyl, 3-pyridyl), C6-C20 aryloxy group (for example, phenoxy, 1-naphthoxy, 2-naph Oxy), acylamino group having 1 to 20 carbon atoms (e.g., acetylamino, benzoylamino), carbamoyl group having 1 to 20 carbon atoms (e.g., N-dimethylcarbamoyl), sulfo group, hydroxyl group, carboxyl group, carbon number 1-20 alkylthio groups (for example, methylthio), a cyano group, etc. are mentioned. Moreover, you may form a ring with another methine group, or you may form a ring with axoxochrome.

Ma ^{1 to} Ma ⁷ are each independently preferably any of a methine group of an unsubstituted, ethyl substituted group or methyl substituted group.

na ¹ and na ² are each independently 0 or 1, and preferably 0. ka ¹ represents an integer of 0 to 3. Preferably it is an integer from 0 to 2, More preferably, it is 1 or 2. When ka ¹ is 2 or more, Ma ³ and Ma ⁴ may be the same or different. Q represents the ion that neutralizes the charge, and y represents the number necessary to neutralize the charge.

In General Formula (3), any one hydrogen atom constituting Za ¹ , Za ² , Ra ¹ , Ra ² , and Ma ^{1 to} Ma ⁷ is removed to form a linking group as a dye residue of General Formula (1). Can be combined with L ¹¹ and L ^2k .

When the chromophore which forms the pigment | dye residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k is a merocyanine pigment | dye, the merocyanine pigment | dye represented by following General formula (4) is preferable.

General formula (4)

In the formula, Za ³ represents an atomic group for forming a 5-membered or 6-membered nitrogen-containing heterocycle, which may be further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring, or the like. . Za ⁴ represents an atomic group forming an acidic nucleus. Ra ³ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group (above preferred examples are the same as Ra ¹ , Ra ² ) It represents either. Ma ^{8 to} Ma ¹¹ each independently represent a methine group (the preferred example is the same as that of Ma ¹ to Ma ⁷ ). na ³ is 0 or 1. ka ² represents an integer of 0 to 3, preferably an integer of 0 to 2. Q represents the ion that neutralizes the charge, and y represents the number necessary to neutralize the charge.

When ka ² is 2 or more, Ma ¹⁰ and Ma ¹¹ may be the same or different. In addition, the formula (4), Za ^3, Za ^{4, 3} Ra, Ma ⁸ in the form ~Ma subtracting any one of the hydrogen atoms constituting ^11, as the dye moiety of the formula (1) linking groups L ¹¹ and L ^2k in Can be combined.

When the chromophore which forms the dye residue represented by Dye ¹¹ , Dye ¹² , and Dye ^2k is an oxonoline pigment | dye, the oxonoline pigment | dye represented by following General formula (5) is preferable.

General formula (5)

In the formula, Za ⁵ and Za ⁶ each independently represent an atomic group for forming an acidic nucleus. Ma ^{12 to} Ma ¹⁴ each independently represent a substituted or unsubstituted methine group (the following preferred examples are the same as Ma ¹ to Ma ⁷ ). ka ³ represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably an integer of 1 to 2. When ka ³ is 2 or more, Ma ¹² and Ma ¹³ may be the same or different.

Q represents the ion that neutralizes the charge, and y represents the number necessary to neutralize the charge.

Further, in the form of removing any one of the hydrogen atoms constituting Za ⁵ , Za ⁶ , Ma ^{12 to} Ma ¹⁴ in the general formula (5), it can be combined with the linking groups L ¹¹ and L ^2k as the dye residues of the general formula (1). have.

As Za ¹ , Za ² and Za ^3, an oxazole nucleus having 3 to 25 carbon atoms (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl, 2-3,4-diethyloxazolyl, 2- 3-methylbenzooxazolyl, 2-3-ethylbenzooxazolyl, 2-3-sulfoethylbenzooxazolyl, 2-3-sulfopropylbenzooxazolyl, 2-3-methylthioethylbenzooxazolyl, 2-3 -Methoxyethylbenzooxazolyl, 2-3-sulfobutylbenzooxazolyl, 2-3-methyl-β-naphthooxazolyl, 2-3-methyl-α-naphthooxazolyl, 2-3-sulfopropyl -β-naphthooxazolyl, 2-3- (3-nathoxyethyl) benzooxazolyl, 2-3,5-dimethylbenzooxazolyl, 2-6-chloro-3-methylbenzooxazolyl, 2-5 -Bromo-3-methylbenzooxazolyl, 2-3-ethyl-5-methoxybenzooxazolyl, 2-5-phenyl-3-sulfopropylbenzooxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzooxazolyl, 2-3-dimethyl-5,6-dimethylthiobenzooxazolyl, thiazole nucleus having 3 to 25 carbon atoms (e.g., 2-3-methylthiazolyl, 2-3- Ethylthiazolyl, 2-3-sul Propylthiazolyl, 2-3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2-3-methylbenzo Thiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl, 2-3-methyl-β-naph Tothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro-3- Methylbenzothiazolyl, 2-6-iodine-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl, 2-5- Phenyl-3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6-dimethylthiobenzothiazolyl, and the like), Imidazole nuclei having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzoimidazolyl, 2-1, 3,4-triethylimida Zolyl, 2-1,3-diethylbenzoimidazolyl, 2-1,3,5-trimethylbenzoimidazolyl, 2-6-chloro-1,3-dimethylbenzoimidazolyl, 2-5,6 -Dichloro-1,3-diethylbenzoimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzoimidazolyl, and the indolenine nucleus having 10 to 30 carbon atoms ( For example, 3,3-dimethylindolenine, a quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl, 2-1-methyl-6-chloro Quinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1-sulfoethyl Quinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, and the like. ), C3-C25 serenazol nucleus (for example, there exist 2-3-methylbenzo serenazolyl etc.), C5-C25 pyridine nucleus (for example, 2-pyridyl etc.), etc. , And also other thiazolin nuclei, oxazoline , Serenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, imidazoline nucleus, imidazo [4,5-quinoxaline] nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus Can be illustrated. These may be substituted, and as substituents, for example, alkyl groups (eg methyl, ethyl, propyl), halogen atoms (eg chlorine, bromine, iodine, fluorine), nitro groups, alkoxy groups (eg methoxy, Ethoxy), aryl groups (eg phenyl), heterocyclic groups (eg 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl), aryloxy groups (eg phenoxy) , Acylamino groups (eg acetylamino, benzoylamino), carbamoyl groups (eg N, N-dimethylcarbamoyl), sulfo groups, sulfonamide groups (eg methanesulfonamide), sulfamoyl groups ( For example, N-methylsulfamoyl), a hydroxyl group, a carboxy group, an alkylthio group (for example, methylthio), a cyano group, etc. are mentioned, Preferably it is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus. These heterocycles may be further condensed. Examples of the ring to be condensed include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring and a thiophene ring.

Za ⁴ , Za ⁵ , and Za ⁶ represent the atomic groups necessary to form acidic nuclei, respectively, and are defined by James, The Theory of the Photographic Process, 4th edition, Mark Milan, p. 198. Specifically, pyrazol-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4- On, 2-oxazoline-5-one, 2-thiooxazolin-2,4-dione, isordanine, rhodanine, thiophen-3-one, thiophen-3-one-1,1-dioxide , Indorin-2-one, indorin-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4- Dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione (e.g. meldrumic acid, etc.), barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione , Indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazoneone, pyrazolopyridone, 3-dicyanomethylidedenyl Nuclei such as -3-phenylpropionitrile, 5- or 6-membered carbocyclic rings (for example, hexane-1,3-dione, pentane-1,3-dione, indan-1,3-dione), and the like. Preferably pyrazole-5-one, barbituric acid, 2-thiobarbituric acid, 1,3-dioxane-4,6-dione .

Specific examples of the cyanine dye, the merocyanine dye, and the oxonol dye include those described in F.M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compoundes, Jhon & Wiley & Sons, New York, London, 1964.

In Formula (1), L ¹¹ and L ^2k each independently represent a divalent linking group, and are not particularly limited except not forming a π-conjugated system between the chromophores to which they are bonded, but preferably an alkylene group (carbon number) 1-20, for example methylene, ethylene, propylene, butylene, pentylene), arylene group (6-26 carbon atoms, for example, phenylene, naphthylene), alkenylene group (2--20, for example Ethenylene, propenylene), alkynylene (2-20 carbon atoms, for example ethynylene, propynylene), -CO-N (R ¹⁰² )-, -CO-O-, -SO ₂ -N (R ¹⁰² )-, -SO ₂ -O-, -N (R ¹⁰³ ) -CO-N (R ¹⁰⁴ )-, -SO _2- , -SO-, -S-, -O-, -CO-, -N ( R ¹⁰⁵ )-and one heterylene group (carbon number 1-26, for example, 6-chloro-1,3,5-triazil-2,4-diyl group and pyrimidine-2,4-diyl group) Or a coupling group having 0 or more and 100 or less, preferably 1 or more and 20 or less carbon atoms formed by combining more than that. R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ each independently represent any one of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. In addition, one or more linking groups represented by L ¹¹ and L ^2k may be present between two chromophores to which they are connected, and a plurality (preferably two) may combine to form a ring.

As L ¹¹ and L ^2k , preferably, two alkylene groups (preferably ethylene) are bonded to each other to form a ring. Especially, when 5- or 6-membered ring (preferably cyclohexyl) is formed, it is more preferable.

In general formula (1), n represents the integer of 0-10, Preferably it is an integer of 0-5, More preferably, it is an integer of 0-3, Especially preferably, it is an integer of 0-2.

In General formula (1), k represents zero or more and all integers of n or less. For example, when n is 2, k represents three integers of 0, 1, and 2, and Dye ^2k and L ^2k each independently represent chromophores of Dye ²⁰ , Dye ²¹ , Dye ²² , and L ²⁰ , L ²¹ and L ²² represent a linking group. When n represents an integer of 2 or more, a plurality of Dye ^2k may be the same or different. In addition, when n represents an integer greater than or equal to 2, some L <^2k> may be same or different.

In General formula (1), Q represents the ion which neutralizes an electric charge, and y represents the number required for neutralizing an electric charge. Whether a compound is a cation, an anion or a substantial ionic charge depends on the substituent of that compound. In the general formulas (1) and (3) to (5), the ions represented by Q may exhibit a cation or an anion depending on the charge of the corresponding dye molecule, and the dye molecule may be electroless. In the case, Q is not present. There is no restriction | limiting in particular in the ion shown as Q, It does not matter whether it is the ion which consists of inorganic compounds, or the ion which consists of organic compounds. In addition, the charge of the ion shown as Q may be monovalent or polyvalent. Examples of the cation represented by Q include sodium ions, metal ions such as potassium ions, quaternary ammonium ions, oxonium ions, sulfonium ions, phosphonium ions, selenium ions, and iodonium ions. . On the other hand, as an anion represented by Q, for example, halogen anions such as chloride ions, bromide ions, fluoride ions, heteropoly acid ions such as sulfate ions, phosphate ions, hydrogen phosphate ions, succinate ions, maleic acid ions, fumaric acid ions, Organic polyanions such as aromatic disulfonic ions, tetrafluoroborate ions, and hexafluorophosphate ions.

As the cation represented by Q, Preferably it is onium ion, More preferably, it is quaternary ammonium ion. Among quaternary ammonium ions, particularly preferably, 4,4'-bipyridinium cation represented by general formula (I-4) of JP 2000-52658 A and JP 2002-59652 A are disclosed. 4,4'-bipyridinium cation.

The cation represented by Q is preferably tetrafluoroborate ions, hexafluorophosphate ions and organic polyanions, and more preferably divalent or trivalent organic anions such as naphthalenedisulfonic acid derivatives. Among the divalent or trivalent organic anions, particularly preferably, they are naphthalenedisulfonic acid anions disclosed in Japanese Patent Application Laid-open No. Hei 10-226170.

Among the dyes represented by the general formula (1), an optical information recording medium containing a dye having a structure represented by the following general formula (6) is preferable.

General formula (6)

In formula, Za <^21> , Za <^22> , Za <^23> , Za <^24> are the atomic groups which independently form an acidic nucleus, and Za <^21> , Za <^22> , Za <^23> , Za <^24> is Za <^5> of the general formula (5) mentioned above, The acidic nucleus demonstrated by Za ⁶ is mentioned as a specific example. Moreover, a preferable example is also the same as Za ⁵ and Za ⁶ mentioned above.

Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , and Ma ²⁶ each independently represent a substituted or unsubstituted methine group, and Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , and Ma ²⁶ are each described above. Is the same as that described in Ma ¹ to Ma ⁷ of General Formula (3).

L ¹¹ is a divalent linking group which does not form a π-conjugated system together with two bonds, and those described in L ¹¹ and L ^2k of General Formula (1) described above may be listed as specific examples. Preferred examples are also the same. Ka ²¹ and Ka ²² each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably an integer of 1 or 2.

When Ka ²¹ and Ka ²² are 2 or 3, plural Ma ²¹ , Ma ²² , Ma ²⁵ , and Ma ²⁶ may be the same or different.

Q represents a monovalent cation that neutralizes charge. Or 2Q to represent a divalent cation. Q can enumerate as a specific example what was demonstrated when Q of General formula (1) is a cation. The same is true of the preferred example.

Moreover, the optical information recording medium whose dye represented by General formula (1) is a dye of the structure represented by General formula (2) is the most preferable.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in General Formula (2) each independently represent any one of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Indicates. As a substituted or unsubstituted alkyl group represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, butyl, i-butyl, t-butyl, i-amyl, cyclopropyl, cyclohexyl, benzyl, phenethyl). When R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each represent an alkyl group, they are linked to each other to form a carbocyclic ring (for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, cyclobutyl). Or cyclooctyl) or a heterocycle (for example, piperidyl, chromanyl, morphoryl, etc.) may be formed. As an alkyl group represented by R <^11> , R <^12> , R <^13> and R <^14> , Preferably, it is a C1-C8 linear alkyl group or a cyclic alkyl group, Most preferably, it is a C1-C5 chain (linear or branched) alkyl group. , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each bonded to form a ring-containing cyclic alkyl group having 1 to 8 carbon atoms (preferably cyclohexyl ring) and a substituted alkyl group having 1 to 20 carbon atoms (eg benzyl, phenethyl )to be.

Examples of the substituted or unsubstituted aryl group represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ in General Formula (2) include an aryl group having 6 to 20 carbon atoms (for example, phenyl and naphthyl). As an aryl group represented by R <^11> , R <^12> , R <^13> and R <^14> , Preferably, it is a C6-C10 aryl group.

The substituted or unsubstituted heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ in General Formula (2) is a 5-6 membered saturated or unsaturated ring composed of carbon atom, nitrogen atom, oxygen atom, or sulfur atom. Heterocyclic group, for example, pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, troazyl group, pyrrolyl group, imidazolyl group, triazolyl group, pranyl group, thiophenyl group, thiazolyl group, oxa A jolyl group, an isothiazolyl group, an isooxazolyl group and the like. Moreover, these may be benzo-substituted (for example, quinolyl group, benzoimidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.). As a substituted or unsubstituted heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , a substituted or unsubstituted heterocyclic group having 6 to 10 carbon atoms is preferable.

As a substituent of the substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group represented by R <^11> , R <^12> , R <^13> and R <^14> of General formula (2), the substituent group mentioned later There is (S).

As a substituent represented by S, a C1-C20 alkyl group (for example, methyl, ethyl, propyl, carboxymethyl, ethoxycarbonylmethyl), a C7-20 aralkyl group (for example, benzyl, phenethyl ), An alkoxy group having 1 to 8 carbon atoms (eg methoxy, ethoxy), an aryl group having 6 to 20 carbon atoms (eg phenyl, naphthyl), an aryloxy group having 6 to 20 carbon atoms (eg Phenoxy, naphthoxy), heterocyclic groups (e.g. pyridyl, pyrimidyl, pyridazyl, benzoimidazolyl, benzothiazolyl, benzooxazolyl, 2-pyrrolidinone-1-yl, 2-piperidone- 1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl, succinimide, phthalimide, maleimide), halogen atoms (e.g. For example, fluorine, chlorine, bromine, iodine), carboxyl group, alkoxycarbonyl group having 2 to 10 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl), cyano group, acyl group having 2 to 10 carbon atoms (e.g. For example, Acetyl, pivaloyl), carbamoyl having 1 to 10 carbon atoms (e.g. carbamoyl, methylcarbamoyl, morpholinocarbamoyl), amino group, substituted amino group having 1 to 20 carbon atoms (e.g., dimethyl Amino, diethylamino, bis (methylsulfonylethyl) amino, N-ethyl-N'-sulfoethylamino), sulfo group, hydroxyl group, nitro group, alkylsulfonylamino group having 1 to 10 carbon atoms (e.g. , Methylsulfonylamino), carbamoylamino group having 1 to 10 carbon atoms (e.g. carbamoylamino, methylcarbamoylamino), sulfonyl group having 1 to 10 carbon atoms (e.g. methanesulfonyl, ethane Sulfonyl), a sulfinyl group having 1 to 10 carbon atoms (for example, methanesulfinyl), and a sulfamoyl group having 0 to 10 carbon atoms (for example, sulfamoyl and methane sulfamoyl). In the case of carboxyl groups and sulfo groups, they may be in a salt state.

R ²¹ , R ²² and R ³ in formula (2) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl Oxy group, substituted or unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted carbamoyl group, amino group, substituted amino group, sul Abandoned, hydroxyl, nitro, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted carbamoylamino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted Either a substituted sulfinyl group or a substituted or unsubstituted sulfamoyl group. R ²¹ , R ²² and R ³ are preferably hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic groups having 2 to 20 carbon atoms, substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms An alkoxy group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 10 carbon atoms Group, substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms, halogen atom is preferred, most preferably hydrogen atom, unsubstituted alkyl group having 1 to 5 carbon atoms, unsubstituted alkoxy group having 1 to 5 carbon atoms, substituted or It is either an unsubstituted C2-C6 heterocyclic group and a halogen atom. R ²¹ , R ²² and R ³ may further have a substituent, and examples of the substituent group (S) described above can be exemplified.

It is preferable that m is 0 and R ²¹ and R ²² are both hydrogen atoms. Moreover, it is preferable that m is 1 and all of R <^21> , R <^22> and R <^3> are hydrogen atoms.

M of General formula (2) represents the integer of 0 or more, Preferably it is an integer of 0-5 (0 or more and 5 or less), More preferably, it is an integer of 0-3, Especially preferably, it is an integer of 0-2 to be.

In general formula (2), when said m is two or more, some R <^3> may be same or different and each independently represents a hydrogen atom or the said substituent.

In General Formula (2), Z ^{x +} represents a cation, and x represents an integer of 1 or more.

As a cation represented by Zx ⁺ , the cation shown by Q of General formula (1) can be illustrated. The cation represented by Z ^{x +} is preferably a quaternary ammonium ion, more preferably 4,4′-bipyridinium cation represented by General Formula (I-4) of JP-A-2000-52658. And 4,4'-bipyridinium cations disclosed in Japanese Patent Laid-Open No. 2002-59652. In General formula (2), x or 1 is preferable.

The pigment | dye represented by General formula (2) of this invention is a novel compound synthesize | combined by the present inventors for the first time.

Although the preferable specific example of the compound represented by General formula (1) or General formula (2) and (6) of this invention is given to the following, this invention is not limited to these.

A general oxosol pigment | dye part can be synthesize | combined by the condensation reaction of the corresponding active methylene compound and a methine source (a compound used for introducing a methine group to a methine dye). Details of this kind of compound are described in Japanese Patent Publication Nos. 39-22069, 43-3504, 52-38056, 54-38129, 55-10059, 58-35544, and Japanese Patents. Publication Nos. 49-99620, 52-92716, 59-16834, 63-316853, 64-40827, and British Patent No. 1133986, US Patent 3247127, 4042397, Reference may be made to the specification of 4181225, 5213956, and 5260179.

As the pigment | dye represented by General formula (3)-(5), the thing of patent documents, such as international publication 02/080161, Unexamined-Japanese-Patent No. 63-209995, and Unexamined-Japanese-Patent No. 2-62279, can be used.

Synthesis of the dye compound represented by the general formula (2) of the present invention can be carried out in accordance with the following scheme.

In addition, when obtaining the pigment | dye part which has more chromophores than pigment | dye part 3-II, the connection part of the said scheme (2) instead of compound 1-I by reaction of compound 3-I and compound 1-I in a scheme. Use 2-I.

The dye compound represented by the said General formula (2) which concerns on this invention may be used by monochromatic, or may use 2 or more types together. Moreover, you may use together the pigment compound which concerns on this invention.

The information recording medium of the present invention is not particularly limited as long as it has a dye compound represented by the general formula (2) as a recording layer. However, when the optical information recording medium of the present invention is applied to a CD-R, the track pitch is 1.4. It is a structure which has in this order the recording layer, the light reflection layer, and the protective layer which contain the pigment compound represented by the said General formula (2) on the transparent disk-shaped board | substrate of thickness 1.2 +/- 0.2mm with pregroove of -1.8 micrometers formed. desirable. In addition, when applied to DVD-R, the following two types are preferable.

(1) A recording layer and a light reflection layer containing a dye compound represented by the above formula (1) are formed on a transparent disk substrate having a thickness of 0.6 ± 0.1 mm with a pregroove having a track pitch of 0.6 to 0.9 µm. An optical information recording medium in which a stack of sheets is bonded to each other so that the recording layer is inward and has a thickness of 1.2 ± 0.2 mm.

(2) A lamination in which a recording layer and a light reflection layer containing the dye compound represented by the general formula (1) are formed on a transparent disk substrate having a thickness of 0.6 ± 0.1 mm having a pregroove having a track pitch of 0.6 to 0.9 µm. And a transparent disc protective substrate of the same shape as the disc shaped substrate of the laminate, the recording layer being bonded to the inside, and having a thickness of 1.2 ± 0.2 mm. In the DVD-R type optical information recording medium, a protective layer may be further formed on the light reflection layer.

The information recording medium of the present invention can be produced, for example, by the method described below. The substrate (including the protective substrate) can be arbitrarily selected from various materials used as substrates of conventional information recording media. As a substrate material, it is glass, for example; Polycarbonate; Acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers; Epoxy resins; Amorphous polyolefin, polyester, etc. are mentioned, You may use together together as needed. In addition, these materials can be used as a film form or a rigid substrate. Among the above materials, polycarbonate is preferred in view of moisture resistance, dimensional stability, price, and the like.

On the substrate surface on the side where the recording layer is formed, a primer layer may be formed for the purpose of improving planarity, improving adhesion and preventing alteration of the recording layer. As the material of the primer layer, for example, polymethyl methacrylate, acrylic acid methacrylic acid copolymer, styrene maleic anhydride copolymer, polyvinyl alcohol, N-metholacrylamide, styrene vinyltoluene copolymer, chlorosulphate High molecular materials such as fonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; And surface modifiers such as silane coupling agents. The primer layer can be formed by dissolving or dispersing the substance in a suitable solvent to prepare a coating liquid, and then applying the coating liquid to the substrate surface by a coating method such as spin coating, dip coating or extrusion coating.

On the substrate (or primer layer), unevenness (pre-groove) indicating information such as a tracking groove or an address signal is formed. The pregroove is preferably formed on the substrate with the track pitch directly when injection molding or extrusion molding a resin material such as polycarbonate. In addition, the pregroove may be formed by forming a pregroove layer. As the material of the pregroove layer, a mixture of at least one monomer (or oligomer) of a monoester, diester, triester and tetraester of acrylic acid and a photopolymerization initiator can be used. The formation of the pregroove layer is, for example, first applying a mixed solution of the acrylic acid ester and the polymerization initiator on a precisely formed model (stamper), and then placing the substrate on the coating liquid layer, and then ultraviolet rays through the substrate or model. The coating layer is cured by irradiating the substrate to fix the substrate and the coating layer. Subsequently, it can obtain by peeling a board | substrate from a model.

On the surface on which the pregroove on the substrate (or primer layer) is formed, a recording layer containing the dye of claim 1, preferably the dye compound represented by the general formula (1) according to the present invention, is formed.

The recording layer may further contain various anti-fading agents for improving light resistance. As a representative example of the anti-fading agent, a metal complex represented by general formula (III), (IV) or (V) described in Japanese Patent Application Laid-Open No. 3-224793, a diimmonium salt, an aluminum salt or Japanese Patent Application Laid-Open No. 2-300287 The nitroso compound shown by Unexamined-Japanese-Patent No. 2-300288, the TCNQ derivative shown by Unexamined-Japanese-Patent No. 10-151861, etc. can be illustrated.

The recording layer is formed by dissolving the dye according to the present invention, and optionally, a quencher, a binder, and the like in a solvent to prepare a coating liquid, and then applying the coating liquid to the substrate surface to form a coating film, followed by drying. This can be done by. As a solvent of the coating liquid for pigment | dye recording layer formation, Ester, such as butyl acetate, ethyl lactate, a cellosolve acetate; Ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; Chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; 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; Fluorine solvents such as 2,2,3,3-tetrafluoropropanol; Glycol ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether, etc. can be illustrated. 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. In the coating liquid, various additives such as antioxidants, UV absorbers, plasticizers and lubricants may be added according to the purpose.

Examples of the binder include, for example, natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin and rubber; Hydrocarbon-based resins such as polyethylene, polypropylene, polystyrene, and polyisobutylene; Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride and polyvinyl acetate copolymer; Acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Synthetic organic polymers such as initial condensates of thermosetting resins such as polyvinyl alcohol, chlorinated polyethylene, epoxy resins, butyral resins, rubber derivatives and phenol-formaldehyde resins. When using a binder together as a material of a recording layer, the usage-amount of a binder generally exists in the range of 0.01-50 times (mass ratio) with respect to a pigment | dye, Preferably it is in the range of 0.1-5 times (mass ratio). The pigment concentration of the coating liquid prepared in this way is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.

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

On the recording layer, a reflective layer is formed for the purpose of improving the reflectance at the time of reproduction of the information. The light reflective material, which is a material of the reflective layer, is a material having high reflectance with respect to laser light, and examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe Metals and semimetals such as, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, etc. Or stainless steel. Preferred among these are Cr, Ni, Pt, Cu, Ag, Au, Al and stainless steel, with Ag being particularly preferred. These substances may be used alone, or in combination of two or more thereof, or as alloys. The reflective layer can be formed on the recording layer, for example, by depositing, sputtering or ion plating the reflective material. The layer thickness of the reflective layer is generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.

On the reflective layer, a protective layer may be formed for the purpose of physically and chemically protecting the recording layer or the like. This protective layer may be formed on the side where the recording layer of the substrate is not formed for the purpose of improving the scratch resistance and the moisture resistance. As the material used for the protective layer, for example, SiO, SiO _2, MgF _2, SnO _2, there can be exemplified an inorganic substance, a thermoplastic resin, a thermosetting resin, an organic material such as UV curable resin, such as Si ₃ N _4. The protective layer can be formed, for example, by laminating an adhesive layer on a reflective layer and / or a substrate on a film obtained by extrusion of plastic. Or it may be formed by a method such as vacuum deposition, sputtering or coating. Moreover, in the case of a thermoplastic resin and a thermosetting resin, after melt | dissolving in these suitable solvents and preparing a coating liquid, it can also be formed by apply | coating this coating liquid and drying. In the case of UV-curable resin, it can be formed by dissolving it as it is or in a suitable solvent to prepare a coating liquid, then applying the coating liquid and irradiating and curing UV light. In these coating liquids, various additives, such as an antistatic agent, antioxidant, and a UV absorber, may also be added according to the objective. The layer thickness of a protective layer generally exists in the range of 0.1-100 micrometers. By the above process, the laminated body in which the recording layer, the reflective layer, and the protective layer was formed as needed on the board | substrate can be manufactured. By producing two laminates as described above and attaching them with an adhesive such that each recording layer is inward, a DVD-R type information recording medium having two recording layers can be produced. The obtained laminate and the disc-shaped protective substrate having substantially the same dimensions as the substrate of the laminate are bonded together with an adhesive such that the recording layer is inward, thereby producing a DVD-R type information recording medium having a recording layer on only one side. can do.

The information recording method of the present invention uses the information recording medium, for example, as follows. First, the recording laser light such as semiconductor laser light is irradiated from the substrate side while the information recording medium is rotated at a predetermined speed or a regular angle speed. By irradiation of this light, a cavity is formed at the interface between the recording layer and the reflective layer (the formation of the cavity is formed with the deformation of the recording layer or the reflective layer or the deformation of both layers), or the substrate is grown in thickness, or Alternatively, it is considered that information is recorded by changing the refractive index due to discoloration, change in the association state, or the like in the recording layer. As the recording light, a semiconductor having an oscillation wavelength in the range of 770 to 790 nm as 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. Laser beams are used. The information recorded as described above can be reproduced by rotating the information recording medium at the same constant speed as described above, irradiating a semiconductor laser light having the same wavelength as that at the time of recording on the substrate side and detecting the reflected light.

(Example)

(Example 1)

Synthesis of Compound (3)

The synthesis of the compound of the present invention was performed according to the above scheme.

[Synthesis of Connecting Part (Compound (1-I))]

Dissolve 1,4-cyclohexadione (22.43 g, 0.2 mol) and malonic acid (41.62 g, 0.4 mol) in acetic anhydride (85 ml), add concentrated sulfuric acid (7.0 ml, 0.12 mol) and stir in an ice bath. It was. As the reaction proceeded, light brown crystals were precipitated, which were filtered and washed with ice-cold distilled water and dried to obtain 8.8'g (yield 15.5%) of light brown crystals of compound (1-I).

[Synthesis of Pigment Part (Compound (3-II))]

Malonic acid (5.2 g, 0.05 mol) and concentrated sulfuric acid (0.5 ml) are added to acetic anhydride (10 ml), and the raw material compound is completely dissolved while stirring at room temperature, followed by 4-ethylcyclohexanone (cooling in an ice bath). 6.31 g, 0.05 mol) was slowly added dropwise. When stirring was continued in an ice bath, colorless crystals were precipitated as the reaction proceeded. Thus, this was filtered, washed with distilled water, and dried to obtain 9.0 g (yield 85.1%) of colorless crystals of the medulric acid derivative. The obtained meldmic acid derivative (4.25 g, 0.02 mol) and N, N'-1,3-pentadien-1-yl-5-iridenyaniline hydrochloride (5.70 g, 0.02 mol) were dissolved in methanol (50 mL). Triethylamine (3.04 g, 0.03 mol) was added to the mixture, and stirring was continued at room temperature. Since purple crystals were precipitated, these were filtered and washed with methanol to obtain purple crystals corresponding to compound (3-I) 5.61 g (yield 76.3%) was obtained. This violet crystal (4.40 g, 12.0 mol) and the compound (1-I) (1.71 g, 6.0 mol) shown in the said synthesis example were dissolved in dimethylformamide (20 mL), and triethylamine (1.82 g, 18 mmol) ) Was added dropwise and stirred at 50 ° C. for 4 hours. Then, distilled water was added to the reaction solution, followed by extraction with ethyl acetate. The extracted organic layer was purified by silica gel column chromatography (dichloromethane / methanol = 6/1) to obtain 2.0 g (yield 39.5%) of purple powder corresponding to compound (3-II).

Synthesis of Pigment Compound

The purple powder (1.24 g, 1.48 mmol) synthesize | combined above was dissolved in the minimum amount of dimethylformamide which melt | dissolves this, the compound C used as a counter cation was added, and it stirred at room temperature. Stirring was continued. Since gold powder precipitated, it was filtered to obtain 0.95 g (yield 48.3%) of gold powder of compound (3).

The obtained gold powder confirmed the structure by 1H NMR.

1 H NMR (DMSO-d6): 0.84 (t, 6H), 1.20 (m, 10H), 1.62 (m, 8H), 1.96-2.14 (m, 12H), 7.11 (m, 4H), 7.24 (d, 2H ), 7.34 to 7.77 (m, 18H), 7.90 (d, 2H), 9.00 (d, 4H), 9.65 (d, 4H), 10.71 (s, 2H)

(Example 2)

Synthesis of Compounds (1), (13) and (14)

In the synthesis method of the compound (3) shown in Example 1, instead of using 4-ethylcyclohexanone, it synthesize | combines using cyclohexanone and refine | purifies using the silica gel column chromatography of the scheme (3). The compound corresponding to the dye anion of 1) and the compound corresponding to the dye anion of Compound (13) or Compound (14) were separated. The compound corresponding to each obtained dye anion was subjected to relative chloride according to the scheme (4) to synthesize Compound (1), Compound (13) and Compound (14).

1 H NMR (DMSO-d 6) of Compound (1): 1.40 (s, 4H), 1.54 (s, 8H), 1.83 (s, 8H), 1.98 (s, 8H), 7.09 to 7.79 (m, 24H), 7.92 (s, 2H), 9.00 (s, 4H), 9.69 (s, 4H)

1 H NMR (DMSO-d 6) of compound (13): 1.41 (s, 4H), 1.53 (s, 8H), 1.82 (s, 8H), 1.98 (s, 24H), 7.13 (t, 8H), 7.27 ( d, 4H), 7.38-7.79 (m, 40H), 7.91 (s, 4H), 9.01 (d, 8H), 9.67 (d, 8H), 10.74 (s, 4H)

(Example 3)

Synthesis of Compound (2)

In the synthesis method of compound (3) shown in Example 1, the compound (2) was synthesized in the same manner as in Example 1 except that 4-methylcyclohexanone was used instead of 4-ethylcyclohexanone.

1 H NMR (DMSO-d6): 0.91 (d, 6H), 1.20 (q, 4H), 1.47 (s, 2H), 1.65 (m, 8H), 2.01 (m, 12H), 7.10 (q, 4H), 7.28 (d, 2H), 7.39-7.86 (m, 18H), 7.89 (s, 2H), 9.01 (d, 4H), 9.67 (d, 4H), 10.71 (s, 2H)

(Example 4)

Synthesis of Compound (4)

In the synthesis method of compound (3) shown in Example 1, the compound (4) was synthesized in the same manner as in Example 1 except that mentone was used instead of 4-ethylcyclohexanone.

1 H NMR (DMSO-d6): 0.81 (t, 12H), 0.90 (d, 8H), 1.21 (t, 2H), 1.41 (t, 4H), 1.61 (t, 4H), 1.72 (d, 2H), 1.97 (s, 8H), 2.18 (d, 4H), 7.12 (q, 4H), 7.24 (d, 2H), 7.38-7.78 (m, 18H), 7.90 (s, 2H), 9.01 (d, 4H) , 9.68 (d, 4H), 10.71 (s, 2H)

(Example 5)

Synthesis of Compound (5)

In the synthesis method of compound (3) shown in Example 1, the compound (5) was prepared in the same manner as in Example 1 except that 3,3,5-trimethylcyclohexanone was used instead of 4-ethylcyclohexanone. Was synthesized.

1 H NMR (DMSO-d6): 0.89 (t, 12H), 0.97 (s, 6H), 1.19 (t, 2H), 1.40 (m, 4H), 1.89-1.98 (m, 16H), 7.11 (m, 4H ), 7.26 (d, 2H), 7.40 (s, 2H), 7.49 (m, 6H), 7.60 (t, 4H), 7.70 (m, 6H), 7.90 (s, 2H), 9.00 (s, 4H) , 9.67 (s, 4H), 10.72 (s, 2H)

(Example 6)

Synthesis of Compound (6)

In the synthesis method of compound (3) shown in Example 1, the compound (6) was synthesized in the same manner as in Example 1 except that methyl ethyl ketone was used instead of 4-ethylcyclohexanone.

1 H NMR (DMSO-d6): 0.95 (t, 6H), 1.53 (s, 6H), 1.81 (t, 4H), 1.99 (s, 8H), 7.11 (q, 4H), 7.26 (d, 2H), 7.39 to 7.77 (m, 18H), 7.89 (s, 2H), 9.00 (d, 4H), 9.67 (d, 4H), 10.69 (s, 2H)

(Example 7)

Synthesis of Compound (7)

In the synthesis method of compound (3) shown in Example 1, the compound (7) was prepared in the same manner as in Example 1 except that 3,3-dimethyl-2-butanol was used instead of 4-ethylcyclohexanone. Synthesized.

1 H NMR (DMSO-d6): 1.10 (s, 18H), 1.51 (s, 6H), 1.98 (s, 8H), 7.14 (q, 4H), 7.28 (d, 2H), 7.38 to 7.78 (m, 18H ), 7.90 (s, 2H), 9.01 (d, 4H), 9.79 (d, 4H), 10.71 (s, 2H)

(Example 8)

Synthesis of Compound (8)

In the synthesis method of compound (3) shown in Example 1, the compound (8) was synthesized in the same manner as in Example 1 except that 2-methyl-3-pentanol was used instead of 4-ethylcyclohexanone. It was.

1 H NMR (DMSO-d6): 0.90 (m, 18H), 1.83 (q, 4H), 2.00 (s, 8H), 2.15 (m, 2H), 7.11 (q, 4H), 7.26 (d, 2H), 7.38 to 7.75 (m, 18H), 7.90 (s, 2H), 9.01 (d, 4H), 9.68 (d, 4H), 10.70 (s, 2H)

(Example 9)

Synthesis of Compound (9)

In the synthesis method of compound (3) shown in Example 1, the compound (9) was synthesized in the same manner as in Example 1 except that diethyl ketone was used instead of 4-ethylcyclohexanone.

1 H NMR (DMSO-d6): 0.85 (t, 12H), 1.84 (q, 8H), 2.00 (s, 8H), 7.11 (q, 4H), 7.26 (d, 2H), 7.32-7.78 (m, 18H ), 7.89 (s, 2H), 9.00 (d, 2H), 9.66 (d, 2H), 10.70 (s, 2H)

(Example 10)

Synthesis of Compound (10)

In the synthesis method of compound (3) shown in Example 1, the compound (10) was synthesized in the same manner as in Example 1 except that 2-pentanol was used instead of 4-ethylcyclohexanone.

1 H NMR (DMSO-d6): 0.90 (t, 6H), 1.39 (m, 4H), 1.45 (s, 6H), 1.77 (m, 4H), 1.98 (s, 8H), 7.10 (q, 4H), 7.27 (d, 2H), 7.40-7.80 (m, 18H), 7.91 (s, 2H), 9.05 (d, 4H), 9.65 (d, 4H), 10.72 (s, 2H)

(Example 11)

Synthesis of Compound (11)

In the synthesis method of compound (3) shown in Example 1, the compound (11) was synthesized in the same manner as in Example 1 except that 3-methylcyclohexanone was used instead of 4-ethylcyclohexanone.

1 H NMR (DMSO-d6): 0.98 (m, 8H), 1.28 (t, 2H), 1.50-1.65 (m, 10H), 1.96-2.08 (m, 12H), 7.11 (m, 4H), 7.25 (d , 2H), 7.38 to 7.73 (m, 18H), 7.90 (s, 2H), 9.00 (s, 4H), 9.66 (s, 4H), 10.70 (s, 2H)

(Example 12)

Synthesis of Compound (12)

In the synthesis method of the compound (3) shown in Example 1, instead of using 4-ethylcyclohexanone, cyclohexanone is substituted with N, N'-1,3-pentadien-1-yl-5-iridenedaniline A compound (12) was prepared in the same manner as in Example 1 except that 3-methyl-N, N'-1,5-heptadien-1-yl-7-iridenyaniline hydrochloride was used instead of using hydrochloride. Synthesized.

1 H NMR (DMSO-d6): 1.41 (s, 4H), 1.58 (s, 8H), 1.82 (s, 8H), 1.99 (s, 8H), 2.17 (s, 6H), 7.24-7.48 (m, 12H ), 7.69-7.99 (m, 12H), 9.00 (s, 4H), 9.68 (s, 4H), 10.71 (s, 2H)

(Example 13)

Evaluation of Optical Constants

The optical properties (real part (n) and false part (k) of complex refractive index) of the dye compound of this invention evaluated the value by the reflection type spectroscopic ellipsometry method. The spin coat film formed on the glass substrate was used for the sample for optical characteristic evaluation used for the spectroscopic ellipsometry. This spin cord film was produced by dissolving each compound in 2,2,3,3-tetrafluoropropanol so as to have a solution concentration of 25 mM, and casting the solution on a rotating glass substrate.

[Production of Comparative Compound (1) -containing Spin Coat Film]

As a comparative example, a spin coat film was produced using Comparative Compound (1) having the following structure having good recording characteristics in 1x recording. In addition, the comparative compound (1) is corresponded to I-94 in Unexamined-Japanese-Patent No. 2002-249674.

Comparative Compound (1)

The optical properties of the spin coat films of Exemplary Compounds (1) and (3) to (14) in the present invention were evaluated, and the values of n and k at 660 nm are shown in Table 1 below from the results obtained.

compound n k Compound (1) 2.24 0.055 Compound (3) 2.23 0.054 Compound (4) 2.20 0.040 Compound (5) 2.20 0.038 Compound (6) 2.27 0.040 Compound (7) 2.22 0.041 Compound (8) 2.24 0.040 Compound (9) 2.25 0.047 Compound (10) 2.26 0.051 Compound (11) 2.21 0.035 Compound (12) 2.21 0.051 Compound (13) 2.40 0.056 Compound (14) 2.30 0.050 Comparative Compound (1) 2.08 0.051

Next, an embodiment as an optical information recording medium is shown.

(Example 14)

[Production of optical record carrier]

By injection molding, the polycarbonate resin was molded into a substrate having a thickness of 0.6 mm and a diameter of 120 mm having a spiral groove (130 nm in depth, 310 nm in width, and 0.74 μm in track pitch).

A coating liquid obtained by dissolving 1.25 g of the dye compound (6) of the present invention in 100 ml of 2,2,3,3-tetrafluoropropanol was prepared, and the coating liquid was prepared on the surface on which the grooves of the substrate were formed by spin coating. It applied and the pigment layer was formed.

Next, silver was sputtered on each dye-coated surface to form a reflective layer having a film thickness of about 150 nm, and then 0.6 mm thick using an ultraviolet curable resin (manufactured by Daicure Clear SD640 Dainippon Ink, Kagaku Kogyo Co., Ltd.) as a welding agent. The disk was made by adhering to the dummy substrate of.

(Comparative Example 1)

A disk was produced in exactly the same manner as in Example 14 except that the comparative compound (1) described above was used instead of the dye compound (6).

(Comparative Example 2)

A disk was produced in exactly the same manner as in Example 14 except that the above comparative compound (1) and the following comparative compound (2) were mixed at a ratio of 6: 4 instead of the pigment compound (6). In addition, the comparative compound (2) is corresponded to I-96 in Unexamined-Japanese-Patent No. 2002-249674.

[Evaluation of Optical Record Media]

Using the DDU1000 and Multi-Signal Generator (Pulse Co., Ltd., laser wavelength = 660nm, aperture ratio = 0.60), it is 8-speed at 1x speed (11.08Mbps), 8x speed (88.64M), and 10x speed (110.8Mbps). 16 modulation signals were recorded.

The recording strategies used are shown in Table 2. In the 1x recording and 10x recording, one type was recorded, and the 8x recording was performed in two types with different pulse widths.

The recording power was set to the recording power at which jitter is the smallest in each medium. Thereafter, reproduction was performed using a laser of the same wavelength as the recording laser wavelength, and jitter was measured. The results are shown in Table 3.

Examples are lower than jitter in all of 1x, 8x, and 10x speeds than the comparative example, and also have high reflectance.

In addition, in the 8X recording characteristic, the jitter was obtained in all of the embodiments with a larger pulse width and a different recording strategy. In addition, when 3T and 14T single frequency signals were recorded at 12x and 16x, the C / N ratio, modulation degree, and jitter equivalent to 1x to 10x were obtained. This indicates that good characteristics can be obtained even at a recording speed equivalent to at least 10 to 16 times or higher.

Record characteristic evaluation result Example 14 Comparative Example 1 Comparative Example 2 Recording speed 1X 8X 8X 10X 1X 8X 8X 10X 1X 8X 8X 10X Record Strategy A B C D A B C D A B C D Optimal recording power (mW) 11 28.5 36.3 33.5 12 29.0 39.0 34.0 7.9 25.5 29.5 29.2 reflectivity(%) 53.2 51.8 52.0 50.9 50 49.1 49.0 48.6 44.5 46.5 44.8 44.4 Jitter (%) 6.1 6.2 6.0 7.2 9.0 13.2 12.0 15.0 8 13.9 6.8 9.0 14T modulation degree 0.54 0.71 0.77 0.76 0.50 0.72 0.76 0.77 0.50 0.73 0.78 0.77 PI error 80 18 11 15 94 40 Not measurable Not measurable 94 Not measurable 90 120 AR (%) 50 32 28 25 48 30 32 25 48 28 28 26

Comparative Compound (2)

(Example 15)

Instead of using the pigment compound (6), a mixture of the pigment compounds 7, 8, 9, 10, 15, 16, 17, 19, 21, 22, Comparative Compound 1, and Comparative Compounds 1 and 2 shown in Table 4 below was used. Disk samples 202 to 213 were produced in exactly the same manner as in Example 14. The recording and reproducing performance was evaluated in exactly the same manner as in Example 14. The results are shown in Table 4. It can be seen that the dye of the present invention has a higher reflectance, a lower jitter, and a sufficient modulation degree than the comparative compound.

Sample Number Pigment Number reflectivity(%) Jitter 14T modulation degree Remarks 201 Compound 6 50.9 7.2 0.76 Invention (Example 14) 202 Compound 7 52.0 8.2 0.78 The present invention 203 Compound 8 51.2 8.1 0.77 The present invention 204 Compound 9 52.2 7.9 0.77 The present invention 205 Compound 10 52.4 8.1 0.78 The present invention 206 Compound 15 53.1 7.8 0.77 The present invention 207 Compound 16 52.1 7.9 0.76 The present invention 208 Compound 17 53.9 8.4 0.75 The present invention 209 Compound 19 52.8 7.6 0.76 The present invention 210 Compound 21 52.1 6.8 0.78 The present invention 211 Compound 22 51.6 8.1 0.78 The present invention 212 Comparative Compound 1 48.6 15.0 0.77 Comparative example 213 Comparative Compounds 1 and 2 44.4 9.0 0.77 Comparative example

Compared with the comparative dye for low-speed recording, the real portion n of the complex refractive index is larger, and the imaginary portion k can provide a pigment of the same or smaller size. An optical information recording medium having excellent recording characteristics from low speed to high speed can be provided.

Claims (4)

An optical information recording medium having two or more chromophores in a molecule, wherein the chromophores contain dyes which are bonded without interposing a conjugated bond. The optical information recording medium according to claim 1, wherein the dye has a structure represented by the following general formula (1). General formula (1) [Dye ¹¹ , Dye ¹² , Dye ^2k each independently represents a pigment residue having a chromophore, L ¹¹ , L ^2k each independently does not form a π conjugated system between the chromophores to which they are bonded N represents an integer of 0 to 10, k represents all integers greater than or equal to 0 and less than n, Q represents ions that neutralize the charge, and y represents the number necessary to neutralize the charge.] The optical information recording medium according to claim 1 or 2, further comprising a dye having a structure represented by the following general formula (6). General formula (6) [In formula, Za <^21> , Za <^22> , Za <^23> , Za <^24> is the atomic group which forms an acidic nucleus each independently, Ma <^21> , Ma <^22> , Ma <^23> , Ma <^24> , Ma <^25> , Ma <^26> are each independently It is a substituted or unsubstituted methine group. L ¹¹ is a divalent linking group that does not form a π conjugate system with two bonds. Ka ²¹ and Ka ²² each independently represent an integer of 0 to 3, respectively. Q represents a monovalent cation that neutralizes charge. Or 2Q to represent a divalent cation. When Ka ²¹ and Ka ²² are 2 or 3, plural Ma ²¹ , Ma ²² , Ma ²⁵ , and Ma ²⁶ may be the same or different.] An oxonol compound represented by the following general formula (2). General formula (2) [Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, and R ²¹ , R ²² , R ³ are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heterocyclic groups , Halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted carbamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted Or an unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted carbamoylamino group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, Of the ring, or unsubstituted alkylsulfinyl group, substituted or unsubstituted aryl sulfinyl group and a substituted or unsubstituted sulfamoyl group represents any. m represents an integer of 0 or more, and when m is 2 or more, some R <^3> may be same or different. Z ^{x +} represents a cation and x represents an integer of 1 or more.]