JP2006289967A - Optical information recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical information recording medium applicable to a blue laser light with improved light resistance and durability not to impair recording/reproduction characteristics. <P>SOLUTION: This optical information recording medium of a heat mode type comprises a recording layer capable of recording information by laser light irradiation with not more than 440 nm wavelength, formed on a substrate, wherein the recording layer containing a methyne coloring matter and an oxidizing agent is formed on the surface of the pregroove-formed side of the transparent disc-like substrate where the pregroove with 0.2 to 0.5 mm track pitch is formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical information recording medium and an information recording method capable of recording and reproducing information using a laser beam, and a novel compound suitable for the same. In particular, the present invention relates to a heat mode type optical information recording medium suitable for recording information using a short wavelength laser beam having a wavelength of 440 nm or less.

  Conventionally, an optical information recording medium (optical disc) capable of recording information only once by laser light is known. This optical disk is also referred to as a recordable CD (so-called CD-R), and its typical structure is a recording layer made of a methine dye on a transparent disk-shaped substrate, a light reflecting layer made of a metal such as gold, and a resin. A protective layer made of a metal is provided in this order in a laminated state. Information recording on the CD-R is performed by irradiating the CD-R with a near-infrared laser beam (usually a laser beam having a wavelength of about 780 nm), and the irradiated portion of the recording layer emits the light. Information is recorded by absorbing and locally raising the temperature, causing a physical or chemical change (eg, pit generation) and changing its optical properties. On the other hand, reading (reproduction) of information is also performed by irradiating a laser beam having the same wavelength as that of the recording laser beam. Information is reproduced by detecting the difference in reflectance from (part).

  Recently, networks such as the Internet and high-definition TV are rapidly spreading. Further, HDTV (High Definition Television) will be broadcast soon, and there is an increasing demand for a large-capacity recording medium for recording image information inexpensively and easily. Although the above-mentioned CD-R and DVD-R capable of high-density recording using a visible laser beam (630 nm to 680 nm) as a recording laser can secure a position as a large-capacity recording medium to a certain extent, Therefore, it cannot be said that the recording capacity is large enough to meet the above requirements. Therefore, development of an optical disc having a higher recording capacity by using a laser beam having a shorter wavelength than that of a DVD-R has been developed. For example, a Blu-ray method using a blue laser of 405 nm An optical recording disk referred to was commercially available.

  Conventionally, in a CD-R type optical disc, as a dye compound contained in the recording layer, for example, a dicarbocyanine dye (having five methine chains) having absorption in the near infrared region, for example, having a benzoindolenin skeleton, Tricarbocyanine dyes (7 methine chains) are advantageously used (Japanese Patent Application Laid-Open Nos. 64-40382 and 64-40387). In order to improve the light resistance, generally, a combination of a singlet oxygen quencher and a cyanine dye as described above is used as an anti-fading agent. For example, nitroso compounds (JP-A-2-300288) and nickel complexes (JP-A-4-146189) are well known as such anti-fading agents.

  Japanese Laid-Open Patent Publication No. 63-64794 proposes an information recording medium with improved light resistance having a recording layer containing a cyanine dye and an electron accepting compound. As a specific example, a tricarbocyanine dye (7 methine chains) having a benzoindolenin skeleton or the like is described as a cyanine dye. On the other hand, as an electron-accepting compound, a tetracarbocyanine dye is described. Cyanoquinodimethane (TCNQ) and tetracyanoethylene are described.

  Similarly, Japanese Patent Application Laid-Open Nos. 10-151861 and 10-324065 propose information recording media having a recording layer containing a cyanine dye and an electron-accepting compound.

  In general, it is known that the absorption maximum wavelength of a dye becomes longer as the spread of the pi-electron system that causes the light absorption is larger. In particular, in the case of cyanine dyes or oxonol dyes that have been put to practical use in many conventional optical disks, the longer the conjugated methine chain length, the longer the wavelength. Therefore, in a blue laser compatible optical recording disk in which the wavelength of the laser beam for recording and reproduction is shorter than that of the DVD-R, the maximum absorption wavelength of the dye is also shorter than that of the dye used in the conventional DVD-R according to the wavelength of the laser light. It is necessary to make the wavelength shorter, and therefore, the conjugated methine chain is shortened, and a cyanine dye having a shorter wavelength is a subject of study. The resulting blue laser compatible optical recording disk has a recording layer with high light resistance. It is important to obtain an information recording medium.

  An object of the present invention is to provide a blue laser light compatible information recording medium with improved light resistance and durability without impairing recording / reproduction characteristics, and an information recording method using the same.

The present inventor conducted a performance comparison between the case where the anti-fading agent of the present invention is present and the case where the anti-fading agent of the present invention is not present in the production of the optical recording disk using the blue laser of 440 nm or less. As a result, it was found that better recording / reproduction characteristics can be obtained when the anti-fading agent of the present invention is present in the recording layer than when the anti-fading agent of the present invention is not present (see “Problems to be Solved by the Invention”). From here).
According to the study of the present inventor, in the combination of a methine dye and an organic oxidant, particularly a combination of a methine dye and an organic oxidant having a reduction potential nobler than −0.6 V, the oxidation potential of the methine dye and the reduction potential of the organic oxidant are When combined so as to have a certain relationship, or when a cyanine dye or oxonol dye having a specific structure is used as a methine dye, the light resistance and durability are remarkably improved without impairing the recording / reproducing characteristics. It has been found that an information recording medium compatible with a blue laser can be manufactured.

Here, the value of the reduction potential of an organic oxidant means the potential at which the organic oxidant is reduced by receiving electron injection at the cathode in voltammetry, while the oxidation potential of a methine dye is voltammetric. Means the potential to be oxidized by emitting electrons at the anode. The oxidation potential and the reduction potential can be accurately measured by this voltammetry method. That is, a voltammogram of an organic oxidant 1 × 10 ⁻³ M is measured in acetonitrile containing 0.1 M tetra-n-propylammonium perchlorate as a supporting electrolyte, and a half-wave potential obtained therefrom is obtained. it can. In addition, platinum is used for the working electrode and a saturated calomel electrode (SCE) is used for the reference electrode, and the measurement is performed at 25 ° C.
A person skilled in the art can easily measure the value of the oxidation potential (Eox). Regarding this method, for example Delahay, “New Instrumental Methods in Electrochemistry” (published by Interscience Publishers, 1954) J. et al. "Electrochemical Methods" by Bard et al. (Published by John Wiley & Sons in 1980) and "Electrochemical Measurement Method" by Akira Fujishima et al. (Published by Gihodo Publishing Co., Ltd. in 1984).

Specifically, the oxidation potential is measured by placing a test sample in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate in the range of 1 × 10 ⁻² to 1 × 10 ⁻⁶ mol / Dissolve in liters and measure as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography. Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone).
In order to uniquely define the potential, in the present invention, cyclic voltammetry is used in acetonitrile containing 0.1 moldm ⁻³ of tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye is 0.001 moldm ⁻³ ). The measured value (vs SCE) is defined as the oxidation potential of the dye.
The object of the present invention is preferably achieved by the following configurations.

[1] An optical information recording medium having a recording layer capable of recording information by irradiating a laser beam of 440 nm or less on a substrate, wherein the recording layer contains a methine dye and an organic oxidant. Information recording medium.
[2] The substrate is a transparent disk-shaped substrate on which a pregroove having a track pitch of 0.2 to 0.5 μm is formed, and the recording layer is provided on the surface on which the pregroove is provided. The heat mode type information recording medium according to [1], wherein
[3] The information recording medium according to [1] or [2], wherein an oxidation potential b volt of the methine dye is in a range of 0.5 <b <1.2.
[4] The information recording medium according to any one of [1] to [3], further including a recording layer containing the organic oxidant having a reduction potential nobler than −0.4 volts.
[5] The information recording medium according to any one of [1] to [4], wherein the organic oxidizing agent is a quaternary ammonium ion or a pyridinium ion.
[6] The information recording medium according to any one of [1] to [5], wherein the organic oxidizing agent is a compound represented by the following general formula (D) or (E).

[Wherein R ⁸¹ and R ⁸² represent an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R ⁸³ and R ⁸⁴ represent a substituent (including a substituent atom). R ⁸⁵ and R ⁸⁶ represent an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ or R ⁸⁵ and R ⁸⁶ may be connected to each other to form a ring. p and q represent an integer of 0 to 4, and when p is 2 or more, R ⁸³ may be the same or different from each other, and when q is 2 or more, R ⁸⁴ may be the same or different from each other. ]
[7] The information recording medium according to any one of [1] to [6], wherein the methine dye is an oxonol dye represented by the general formula (CI).
General formula (CI)

[Wherein, A, B, C and D represent an electron-withdrawing group, and A and B or C and D may be linked to each other to form a ring. This is an electron-withdrawing group in which the sum of the Hammett σp values and the sum of the Hammett σp values of C and D are each 0.6 or more. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. ]
The combination of the oxonol dye represented by the general formula (CI) and the compound represented by the general formula (D) or (E) described in [8] is preferable, and the compound represented by the general formula (D) Is more preferable.
[8] The methine dye is an oxonol dye represented by general formula (C-II), general formula (C-III), or general formula (C-IV) [1] to [7] ] The information recording medium in any one of.
Formula (C-II)

Formula (C-III)

Formula (C-IV)

[Wherein, C and D represent an electron-withdrawing group, which may be linked to each other to form a ring, and when not linked to each other, the sum of the Hammett σp values of C and D is 0.6 or more. It is an electron withdrawing group. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. Y is either —O— or —NR ¹ — or —CR ² R ³ —, R ¹ , R ² , R ³ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a substituent, and Z Represents a substituted or unsubstituted alkylene group, and x represents 1 or 2. ]
[9] The methine dye is an oxonol dye represented by the general formula (CV) or the general formula (C-VI), according to any one of [1] to [7]. Information recording media.
General formula (C-V)

Formula (C-VI)

[Wherein, C and D represent an electron-withdrawing group, which may be linked to each other to form a ring, and when not linked to each other, the sum of the Hammett σp values of C and D is 0.6 or more. It is an electron withdrawing group. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. R ^{4 to} R ⁷ each independently represents a hydrogen atom or a substituent, and G represents an oxygen atom or a sulfur atom. ]
[10] The information recording medium according to any one of [7] to [9], wherein the m ⁷¹ is 0.
[11] The information recording medium according to any one of [1] to [4], wherein the organic oxidant is a compound represented by the following general formula (A).
Formula (A):

[Wherein, X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, ═NR ¹ group, or ═CR ² R ³ group, and m and n are 0 to 3 such that m + n ≧ 2. R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and L ¹ and L ² each independently represent a divalent linking group. ]
[12] The information recording medium according to [11], wherein the organic oxidant is a compound represented by the following general formula (AI).
General formula (AI):

[Wherein, X ¹¹ and X ¹² each independently represent an oxygen atom, a sulfur atom, ═NR ⁸ group, or ═CR ⁹ R ¹⁰ group, and R ⁸ , R ^9, and R ¹⁰ each independently represent a hydrogen atom or a substituent R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ are connected to form an unsaturated condensed ring. You may do it. ]
[13] The information recording medium as described in [11] or [12], wherein the organic oxidizing agent is a compound represented by the following general formula (A-II).
Formula (A-II):

[Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent, and R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ are linked to form an unsaturated condensed ring. You may do it. ]
[14] The information recording medium according to [1], wherein the methine dye is a cyanine dye represented by the following general formula (BI).

[Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocycle, and R ³⁰ and R ³¹ may be independently substituted. Represents a good alkyl group, L ³ represents an optionally substituted methine group, M 1 represents a charge neutralizing counter ion, and m 1 represents a number of 0 or more necessary to neutralize the charge in the molecule. To express. "
[15] The [14], wherein the methine dye is a cyanine dye represented by the following general formula (B-II), general formula (B-III), or general formula (B-IV): Information recording media.

[Wherein, Z ¹¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle optionally having substituent (s), and R ¹¹² and R ¹¹³ are each independently an alkyl group, ^Represents an aryl group, an aralkyl group or a heterocyclic group, L ¹² and L ¹³ each independently represent a methine group ^optionally having a substituent, X ⁿ²⁻ represents an organic or inorganic ^n- valent anion, n2 represents an integer of 1 to 5. ]

[In the formula, Z ²¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may have a substituent, and R ²² and R ²³ are each independently an alkyl group, An aryl group, an aralkyl group or a heterocyclic group is represented, and L ²² and L ²³ each independently represent a methine group which may have a substituent. ]

[In the formula, Z ³¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a substituent, and R ³² each independently represents an alkyl group, an aryl group, An aralkyl group or a heterocyclic group, R ³³ and R ³⁴ each independently represent an alkyl group, an aralkyl group or a heterocyclic group, and R ³³ and R ³⁴ may be linked to form a ring. L ³² and L ³³ each independently represent a methine group ^optionally having a substituent, X ⁿ³⁻ represents an organic or inorganic n3-valent anion, and n3 represents an integer of 1 to 5. ]
A cyanine dye represented by the general formula (B-II), the general formula (B-III) or the general formula (B-IV); and the general formula (A) described in [4] (preferably described in [5] In general formula (AI), more preferably combined with general formula (A-II) described in [6].
[16] In an optical information recording medium having a recording layer capable of recording information by irradiating a laser beam of 440 nm or less on a substrate, a transparent disk having a pregroove with a track pitch of 0.2 to 0.5 μm The surface of the substrate on which the pregroove is provided includes a methine dye and an organic oxidant having a reduction potential nobler than −0.4 volts, and the oxidation potential b volts of the methine dye and the reduction of the organic oxidant. A heat mode type [1] to [15] characterized in that a recording layer is provided in which the difference from the potential a volts satisfies the relational expression of 0 <b−a <1.6. An information recording medium according to any one of the above.

  By combining the methine dye and organic oxidant contained in the recording layer so that the potential difference between them and the specific chemical structure have a specific relationship, the recording / reproduction characteristics are not impaired, and high light resistance even after recording In addition, an information recording medium capable of recording information by irradiation with a laser beam of 440 nm or less and having storage stability under high temperature and high humidity can be manufactured.

  The present invention is an information recording medium having a recording layer capable of recording information on a substrate by irradiation with a laser beam of 440 nm or less.

  The present invention preferably has the following aspects. The information recording medium of the present invention has a recording layer containing a methine dye and an organic oxidizing agent on a transparent disk-like substrate on which pregrooves having a track pitch of 0.2 to 0.5 μm are formed. The organic oxidant used in the present invention is a compound whose reduction potential a (V) is nobler than −0.4V. The reduction potential a (V) of the organic oxidant is -0.4 <a <0.5 (preferably -0.4 <a <0.2, more preferably -0.4 <a <-0. .1) is preferable. On the other hand, the oxidation potential b (V) of the methine dye is 0.5 <b <1.2 (preferably 0.6 <b <1.1, more preferably 0.6 <b <1.0). It is preferable that it exists in the range.

  In the present invention, the difference between the oxidation potential a (V) of the methine dye and the reduction potential b (V) of the organic oxidant is such that 0 <b− A <1.6 (preferably 0.4 <ba <1.5, more preferably 0.7 <ba <1.4) is used in combination so as to satisfy the relational expression. It is particularly preferable that the relational expression of 1.0 ≦ b−a ≦ 1.3 is satisfied.

Further, in the present invention, the specific organic oxidant as described above and the methine dye are represented by the following formulas (BI), (B-II), (B-III), and (B It is preferable to use in combination with a cyanine dye represented by -IV) or an oxonol dye represented by the general formula (CI). Furthermore, organic oxidants represented by the general formula (A) (preferably the general formula (AI), more preferably the general formulas (A-II), (A-III), (A-IV)) and the general It is more preferable to use a cyanine dye represented by formula (B-II), general formula (B-III), or general formula (B-IV) in combination.
It is more preferable to use a combination of the organic oxidant represented by the general formula (D) or the general formula (E) and the oxonol dye represented by the general formula (CI).
Furthermore, the organic oxidant represented by the general formula (D) or the general formula (E), the general formula (C-II), the general formula (C-III), the general formula (C-IV), the general formula (C- V) or an oxonol dye represented by formula (C-VI) is particularly preferably used in combination.

Hereinafter, the organic oxidizing agent and methine dye used in the present invention will be described.
First, the preferable organic oxidizing agent used with respect to a methine dye is demonstrated. The organic oxidant used for the methine dye is preferably a carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds, or a quaternary ammonium ion or pyridinium ion, and a carbon having a plurality of exocyclic double bonds. A ring or heterocyclic compound or a pyridinium ion is more preferable.
When the methine dye is a cyanine dye, the organic oxidant to be combined is a carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds (preferably the general formula (A) (preferably the general formula (AI), Organic oxidants represented by general formulas (A-II), (A-III) and (A-IV)) are preferred.
When the methine dye is an oxonol dye, the organic oxidant to be combined is preferably a quaternary ammonium ion or a pyridinium ion, preferably a pyridinium ion (preferably an organic oxidant represented by the general formula (D) or the general formula (E)). It is more preferable that
Methine dye

  A carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds will be described. Examples of atoms constituting the ring include nitrogen, oxygen, sulfur and selenium in addition to carbon. In the present invention, examples of the carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds include compounds represented by the following general formula (A).

In the formula, X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a ═NR ¹ group, or a ═CR ² R ³ group. m and n represent an integer of 0 to 3 such that m + n ≧ 2. R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. L ¹ and L ² each independently represent a divalent linking group.

Hereinafter, the organic oxidizing agent represented by the general formula (A) will be described in detail. In the general formula (A), it is preferable that m and n are both 1. The substituent represented by the above R ¹ , R ² and R ³ is a halogen atom or a substituent formed by combining a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Examples of substituents include alkyl groups, alkenyl groups, aralkyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups, mercapto groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyloxy groups. , Amino group, alkylamino group, amide group, sulfonamido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group , Alkylsulfinyl group, sulfamoyl group, carboxyl group (including salt), and sulfo group (including salt). These may be further substituted with these substituents.

Examples of substituents represented by R ¹ , R ² and R ³ will be described in more detail.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The alkyl group is an alkyl group which may have a linear, branched or cyclic substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, methyl, ethyl, propyl, isopropyl , T-butyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 3-methoxypropyl, 2-aminoethyl, acetamidomethyl, 2-acetamidoethyl, carboxymethyl, 2-carboxyethyl, Examples include 2-sulfoethyl, ureidomethyl, 2-ureidoethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, hexadecyl, and octadecyl. The alkenyl group is a linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and examples thereof include vinyl, allyl, 1-propenyl, 2-pentenyl, 1,3- Mention may be made of butadienyl, 2-octenyl and 3-dodecenyl.

  The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and examples thereof include benzyl. The aryl group is an aryl group having 6 to 10 carbon atoms which may have a substituent, and examples thereof include phenyl, naphthyl, p-dibutylaminophenyl, and p-methoxyphenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and the number of heteroatoms constituting the ring and the type of element May be one or more, for example, furyl, benzofuryl, pyranyl, pyrrolyl, imidazolyl, isoxazolyl, pyrazolyl, benzotriazolyl, pyridyl, pyrimidyl, pyridazinyl, thienyl, indolyl, quinolyl, phthalazinyl, quinoxalinyl, pyrrolidinyl, Examples include pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, indolinyl, morpholinyl.

  The alkoxy group is an alkoxy group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms). For example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, 2-methoxyethoxy Examples include 2-methanesulfonylethoxy, pentyloxy, hexyloxy, octyloxy, undecyloxy, dodecyloxy, hexadecyloxy, and octadecyloxy. The aryloxy group is an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenoxy and p-methoxyphenoxy. The alkylthio group is an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methylthio, ethylthio, octylthio, undecylthio, dodecylthio, hexadecylthio, and octadecylthio. The arylthio group is an arylthio group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenylthio and 4-methoxyphenylthio. The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include acetoxy, propanoyloxy, pentanoyloxy, octanoyloxy, dodecanoyloxy, and octadecanoyloxy. it can.

  The alkylamino group is an alkylamino group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methylamino, dimethylamino, diethylamino, dibutylamino, octylamino, dioctylamino, and undecylamino. be able to. The amide group is an amide group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms). For example, acetamido, acetylmethylamino, acetyloctylamino, acetyldecylamino, acetylundecylamino, acetyloctadecylamino, Examples include noylamino, pentanoylamino, octanoylamino, octanoylmethylamino, dodecanoylamino, dodecanoylmethylamino, and octadecanoylamino. The sulfonamide group is a sulfonamide group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), such as methanesulfonamide, ethanesulfonamide, propylsulfonamide, 2 -Methoxyethylsulfonamide, 3-aminopropylsulfonamide, 2-acetamidoethylsulfonamide, octylsulfonamide, undecylsulfonamide can be mentioned.

The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and examples thereof include methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino, and undecyloxycarbonylamino. be able to. The alkoxysulfonylamino group is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methoxysulfonylamino, ethoxysulfonylamino, octyloxysulfonylamino, and undecyloxysulfonylamino. be able to. The sulfamoylamino group is a sulfamoylamino group having 0 to 18 carbon atoms (preferably 0 to 6 carbon atoms), such as methylsulfamoylamino, dimethylsulfamoylamino, ethylsulfamoylamino, Mention may be made of propylsulfamoylamino, octylsulfamoylamino, undecylsulfamoylamino.

  The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), such as ureido, methylureido, N, N-dimethylureido, octylureido. And undecylureido. The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms). For example, thioureido, methylthioureido, N, N-dimethylthioureido, octylthio Examples include ureido and undecylthioureido. The acyl group is an acyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include acetyl, benzoyl, octanoyl, decanoyl, undecanoyl, and octadecanoyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and examples thereof include methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl, and undecyloxycarbonyl.

  The carbamoyl group is a carbamoyl group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), such as carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, Examples thereof include N-octylcarbamoyl, N, N-dioctylcarbamoyl, and N-undecylcarbamoyl. The alkylsulfonyl group is an alkylsulfonyl group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), such as methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl, octanesulfonyl. And undecanesulfonyl. The alkylsulfinyl group is an alkylsulfinyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methanesulfinyl, ethanesulfinyl, and octanesulphinyl. The sulfamoyl group is a sulfamoyl group which may have a substituent having 0 to 18 carbon atoms (preferably 0 to 6 carbon atoms), for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, octylsulfa Mention may be made of moyl, dioctylsulfamoyl and undecylsulfamoyl.

L ¹ and L ² each independently represents a divalent linking group. Here, the divalent linking group is composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and constitutes a 4- to 8-membered ring together with the carbon atom to which X ¹ and X ² are bonded. Specific examples of L ¹ and L ² include -C (R ⁴ ) (R ⁵ )-, -C (R ⁶ ) =, -N (R ⁷ )-, -N =, -O-, and -S. Examples thereof include a divalent linking group constituted by combining-. Here, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituent, the details of which are the same as those described for R ¹ , R ² and R ³ . The 4- to 8-membered ring may form a saturated or unsaturated condensed ring, and examples of the condensed ring include a cycloalkyl ring, an aryl ring, and a heterocyclic ring. It is synonymous with what was demonstrated by said R < ¹ >, R < ² > and R < ³ >.

  The 4- to 8-membered ring will be described in more detail. Examples of the 4-membered ring include cyclobutanedione, cyclobutenedione, and benzocyclobutenequinone. Examples of 5-membered rings include cyclopentanedione, cyclopentenedione, cyclopentanetrione, cyclopentenetrione, indandione, indantrione, tetrahydrofurandione, tetrahydrofurantrione, tetrahydropyrroledione, tetrahydropyrroletrione, tetrahydrothiophenedione, tetrahydrothiophenetrione. Can be mentioned. Examples of 6-membered rings include benzoquinone, quinomethane, quinodimethane, quinoneimine, quinonediimine, thiobenzoquinone, dithiobenzoquinone, naphthoquinone, anthraquinone, dihydrochromendione, dihydropyridinedione, dihydropyrazinedione, dihydropyrimidinedione, dihydropyridazinedione, dihydrophthalazine Mention may be made of diones, dihydroisoquinolinediones, tetrahydroquinolinetriones.

Examples of the 7-membered ring include cycloheptanedione, cycloheptanetrione, azacycloheptanetrione, diazacycloheptanetrione, oxocycloheptanetrione, dioxocycloheptanetrione, oxoazacycloheptanetrione. Examples of 8-membered rings include cyclooctanedione, cyclooctanetrione, azacyclooctanetrione, diazacyclooctanetrione, oxocyclooctanetrione, dioxocyclooctanetrione, oxoazacyclooctanetrione, cyclooctenedione, cyclooctanedione Examples include dienedione and dibenzocyclooctenedione. The ring formed by L ¹ and L ² together with the carbon atom to which X ¹ and X ² are bonded is preferably a 6-membered ring.

  The carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds is more preferably a compound represented by the following general formula (AI).

In the formula, X ¹¹ and X ²² each independently represent an oxygen atom, a sulfur atom, ═NR ⁸ , or ═CR ⁹ R ¹⁰ . R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent. = NR ⁸ and = CR ⁹ R ¹⁰ represented by X ¹¹ and X ²² are synonymous with = NR ¹ and = CR ² R ³ represented by X ¹ and X ² in the general formula (A), respectively. The preferred range is also the same. The substituents represented by R ⁸ , R ⁹ and R ¹⁰ are synonymous with the substituents represented by R ¹ , R ² and R ³ in the general formula (A), and their preferred ranges are also the same. is there. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. When R ¹¹ and R ¹² , or R ¹³ and R ¹⁴ simultaneously become a substituent, they may be linked to each other to form an unsaturated condensed ring. This unsaturated condensed ring may have a substituent, and examples of the substituent include the same as those described above for R ^{1 to} R ³ .

The ^{X 11} and ^{X 22} are each independently preferably an oxygen atom or ⁼ CR ^{9 R 10} group, and more preferably both of the oxygen atoms or together ⁼ CR ^{9 R 10} group. Here, R ⁹ and R ¹⁰ are preferably each independently a halogen atom, a cyano group, an acyl group, an alkoxycarbonyl group, or an alkylsulfonyl group. A case where X ¹¹ and X ²² are both oxygen atoms will be described.
When X ¹¹ and X ²² are both oxygen atoms, it is more preferable that at least two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are electron-withdrawing groups. Here, the electron-withdrawing group means a substituent having a positive Hammett σp value, specifically, a halogen atom, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, Or an alkylsulfinyl group can be mentioned. As a particularly preferred combination when X ¹¹ and X ²² are both oxygen atoms, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a nitro group, Alkoxy, alkylthio, amino, alkylamino, amide, sulfonamido, sulfamoylamino, alkoxycarbonylamino, alkoxysulfonylamino, ureido, thioureido, acyl, alkoxycarbonyl, carbamoyl A group, an alkylsulfonyl group, an alkylsulfinyl group, and a sulfamoyl group, of which at least two are electron-withdrawing groups.

As the most preferred combination, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, carbon C1-C6 alkylthio group, C1-C6 amide group, C1-C6 sulfonamide group, C1-C6 ureido group, C1-C6 acyl group, C2-C6 An alkoxycarbonyl group, a carbamoyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, and an alkylsulfinyl group having 1 to 6 carbon atoms, at least two of which are a halogen atom, a cyano group, and an alkylsulfonyl group Group or an alkylsulfinyl group.

When X ¹¹ and X ²² are both ═CR ⁹ R ¹⁰ groups, the carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds is a compound represented by the following general formula (A-II): More preferably.

^{Wherein, R 15, R 16, R} 17, and ^{R 18} are each independently has the same meaning as those described in relation to ^R 11 ^{to R 14.}

  The carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds is particularly preferably a compound represented by the following general formula (A-III) or general formula (A-IV).

In the formula, R ¹⁹ represents a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group, a ureido group, an acyl group, or an alkoxycarbonyl group. R ²⁰ means the same as described in R ^{1 to} R ³ . m4 represents an integer of 1 to 4, and when m4 or 4-m4 represents an integer of 2 or more, the plurality of R ¹⁹ and the plurality of R ²⁰ may be the same or different.

In the formula, R ²¹ represents a hydrogen atom or a substituent. Here, the substituent means the same as those described in the R ¹ to R ^3. m5 represents an integer of 0 to 6, and when m5 represents an integer of 2 or more, the plurality of R ²¹ may be the same or different.

In the general formula (A-III), a preferable combination of R ¹⁹ and R ²⁰ will be described. R ¹⁹ is a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms, and R ²⁰ is a hydrogen atom or 1 to 6 carbon atoms. The combination which is an alkyl group is preferable, and the most preferable combination is that R ¹⁹ is an alkoxy group having 1 to 6 carbon atoms and R ²⁰ is a hydrogen atom.

In the general formula (A-IV), R ²¹ is preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group, a ureido group, or an acyl group. Preferably, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an amide group having 1 to 6 carbon atoms, and the number of carbon atoms A sulfonamide group having 1 to 6 carbon atoms, a ureido group having 1 to 6 carbon atoms, and an acyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, A bromine atom, a cyano group, and an alkoxy group having 1 to 6 carbon atoms, and most preferably a hydrogen atom.

  Specific examples of the carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds, which are organic oxidizing agents for the methine dye used in the present invention, include organic compounds described in JP-A-10-151861 and JP-A-10-324065. Although an oxidizing agent or the following compound is mentioned, it is not limited to these.

  The pyridinium ion will be described. Examples of the pyridinium ion include N-alkylpyridinium, N-alkenylpyridinium, N-alkynylpyridinium, and N-arylpyridinium. More specifically, the substituted or unsubstituted N-alkylpyridinium having 1 to 60 carbon atoms, the substituted or unsubstituted N-alkenylpyridinium having 1 to 60 carbon atoms, and the substituted or unsubstituted N-alkynylpyridinium having 1 to 60 carbon atoms. And substituted or unsubstituted N-arylpyridinium having 1 to 60 carbon atoms.

  The pyridinium ion is preferably a compound represented by the general formula (D) or the general formula (E).

The general formula (D) or the general formula (E) will be described. The alkyl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is preferably a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably 1 carbon atom. To 8 substituted or unsubstituted linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, cyclohexyl, cyclopropyl and the like. Can be mentioned. Examples of the substituent of the alkyl group include a halogen atom (eg, F, Cl, Br, etc.), an alkoxy group having 1 to 18 carbon atoms, preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy, ethoxy, etc.), 10 aryloxy groups (eg, phenoxy, p-methoxyphenoxy, etc.), alkylthio groups having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, etc.), arylthio groups having 6 to 10 carbon atoms (Eg, phenylthio, etc.), acyl groups having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg, acetyl, propionyl, etc.), acyloxy groups having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg, , Acetoxy, propionyloxy, etc.), an alkoxycarbonyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxy) Alkenyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg vinyl), alkynyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg ethynyl etc.), Aryl groups having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), aryloxycarbonyl groups having 7 to 11 carbon atoms (eg, naphthoxycarbonyl, etc.), 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms Amino group (eg, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methyl Carbamoylamino, phenylcarbamoylamino, a Tilamino, ethylcarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino, etc.), carbamoyl groups having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, Ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.), sulfamoyl groups having 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms (eg, unsubstituted sulfamoyl, methyl Sulfamoyl, phenylsulfamoyl, etc.), cyano group, nitro group, carboxy group, hydroxyl group, heterocyclic group (eg, oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benz) Imidazole, indolenine, pyridine, sulfolane, furan, thiophene, pyrazole, pyrrole, chroman, coumarin, etc.).

The alkenyl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is a substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Preferable examples include vinyl, allyl, isopropenyl, 1-propenyl, 1,3-butadienyl, cyclohexenyl and the like. The substituent for the alkenyl group has the same meaning as the substituents for the alkyl group other than the alkenyl group.

The alkynyl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is a substituted or unsubstituted linear, branched or cyclic alkynyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Preferable examples include ethynyl and 2-propynyl. The substituent for the alkynyl group has the same meaning as the substituents for the alkyl group other than the alkynyl group.

The aryl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl and naphthyl. Can be mentioned. The substituent for the aryl group has the same definition as the substituent for the alkyl group, and examples of the substituent further include an alkyl group (eg, methyl, ethyl, etc.).

R ⁸¹ and R ⁸² may be connected to each other to form a ring. In the case of forming a ring, it is preferable that carbon atoms in R ⁸¹ and R ⁸² , carbon atoms and hetero atoms, or hetero atoms are bonded to each other. More preferably, they are carbon atoms, and particularly preferably, they are bonded by methylene groups.

R ⁸⁵ and R ⁸⁶ are preferably connected to each other to form a ring. The formed ring is preferably a 5-, 6- or 7-membered ring, more preferably a 6-membered ring. When a ring is formed, a ring is formed by bonding of carbon atoms in R ⁸⁵ and R ⁸⁶ , or a carbon atom and a hetero atom or hetero atoms, preferably, carbon atoms in R ⁸⁵ and R ⁸⁶ are bonded to each other. This is due to the combination of More preferably, it is a ring formed by bonding of methylene groups.

The substituent represented by R ⁸³ or R ⁸⁴ is, for example, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (for example, methyl, ethyl, etc.). Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl, acetoxyethyl, etc.), preferably 7 to 18 carbon atoms, Is a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl, carboxybenzyl, etc.), an alkenyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (for example, vinyl), 2 carbon atoms To 18 and preferably alkynyl groups having 2 to 8 carbon atoms (eg, ethynyl, etc.) A substituted or unsubstituted aryl group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, etc.) A substituted or unsubstituted acyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (for example, acetyl, propionyl, butanoyl, chloroacetyl, etc.), 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms A substituted or unsubstituted sulfonyl group (for example, methanesulfonyl, p-toluenesulfonyl, etc.), an alkoxycarbonyl group having 2 to 18, preferably 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, etc.), carbon number An aryloxycarbonyl group having 7 to 18, preferably 7 to 12 carbon atoms (eg , Phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenylcarbonyl and the like), a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (for example, methoxy, ethoxy, n-butoxy, Methoxyethoxy, etc.), substituted or unsubstituted aryloxy groups having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, etc.), 2 to 18 carbon atoms, preferably 2 carbon atoms To 8 substituted or unsubstituted acyloxy groups (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.), substituted or unsubstituted 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms Sulfonyloxy group (for example, methane Sulfonyloxy, etc.), a carbamoyloxy group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (for example, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), a substitution having 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms, Unsubstituted amino group (for example, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonyl Amino, methylcarbamoylamino, phenylcarbamoylamino, ethylthiocarbamoylamino, methylsulfamoylamino, phenylsulfamoylamino, acetylamino, ethylcarbonylamino , Ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino, benzenesulfonylamino, etc.), a substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms ( For example, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.), substituted with 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms Or an unsubstituted sulfamoyl group (for example, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a hydroxyl group, a nitro group, a cyano group , Carboxyl group, heterocyclic group and the like.

The substituent represented by R ⁸³ or R ⁸⁴ is preferably a hydrogen atom or an alkyl group. Particularly preferably, both are hydrogen atoms.

R ⁸³ and R ⁸⁴ may be connected to each other to form a carbocyclic or heterocyclic ring. Preferably, it is a carbocyclic ring, more preferably a condensed aromatic ring with a pyridine ring bonded to each of R ₃ and R ₄ .

  Examples of the quaternary ammonium ions represented by the above general formula (D) and general formula (E) include compounds described in JP-A-10-109475, JP-A-10-297103, and JP-A-2001-63211. However, it is not limited to these.

Next, the methine dye used in the present invention will be described. Usable methine dyes include, for example, cyanine dyes, merocyanine dyes, phthalocyanine dyes, oxonol dyes, pyrylium dyes, thiopyrylium dyes, triarylmethane dyes, polymethine dyes, squalium dyes, and azurenium dyes. Examples thereof include dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, indoaniline dyes, aminium dyes / diimmonium dyes, and pyran dyes.
In the present invention, a cyanine dye represented by the following general formula (BI), general formula (B-II), general formula (B-III), or general formula (B-IV) or the following general formula (C- It is preferable to use an oxonol dye represented by I).
Formula (BI)

[Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocycle, R ³⁰ and R ³¹ each independently represent an alkyl group, L ³ , L ⁴ and L ⁵ each independently represents a methine group, M 1 represents a charge neutralizing counter ion, and m 1 represents a number of 0 or more necessary for neutralizing the charge in the molecule. ]

[Wherein, Z ¹¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle optionally having substituent (s), and R ¹¹² and R ¹¹³ are each independently an alkyl group, ^Represents an aryl group, an aralkyl group or a heterocyclic group, L ¹² and L ¹³ each independently represent a methine group ^optionally having a substituent, X ⁿ²⁻ represents an organic or inorganic ^n- valent anion, n2 represents an integer of 1 to 5. ]

[In the formula, Z ²¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may have a substituent, and R ²² and R ²³ are each independently an alkyl group, An aryl group, an aralkyl group or a heterocyclic group is represented, and L ²² and L ²³ each independently represent a methine group which may have a substituent. ]

[In the formula, Z ³¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a substituent, and R ³² each independently represents an alkyl group, an aryl group, An aralkyl group or a heterocyclic group, R ³³ and R ³⁴ each independently represent an alkyl group, an aralkyl group or a heterocyclic group, and R ³³ and R ³⁴ may be linked to form a ring. L ³² and L ³³ each independently represent a methine group ^optionally having a substituent, X ⁿ³⁻ represents an organic or inorganic n-valent anion, and n represents an integer of 1 to 5. ]
General formula (CI)

[Wherein, A, B, C and D represent an electron-withdrawing group, and A and B or C and D may be linked to each other to form a ring. This is an electron-withdrawing group in which the sum of the Hammett σp values and the sum of the Hammett σp values of C and D are each 0.6 or more. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. ]

The cyanine dye represented by formula (BI) will be described in detail below.
Z ¹ and Z ² each independently represents an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring. The nucleus formed by Z ¹ and Z ² includes 3,3-dialkylindolenin nucleus, 3,3-dialkylbenzoindolenine nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, thiazoline nucleus, oxazole nucleus, benzo Oxazole nucleus, naphthoxazole nucleus, oxazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthselenazole nucleus, selenazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, naphthotelrazole nucleus, tellurazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphtho Examples thereof include an imidazole nucleus, a pyridine nucleus, a quinoline nucleus, an isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. The 5-membered or 6-membered nitrogen-containing heterocyclic ring mentioned here may have a substituent, if possible, and the substituent is R ¹ described in the general formula (A). , R ² and R ³ can be mentioned.

  Examples of the substituent will be described in more detail. The alkyl group is an alkyl group which may have a linear, branched or cyclic substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), for example, methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, pentyl, 2-hydroxyethyl, 4-carboxybutyl, hexyl, octyl, benzyl and phenethyl. The alkenyl group is a linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms), such as vinyl, allyl, 1-propenyl, 2-pentenyl, 1,3-butadienyl, and 2-octenyl can be mentioned.

  The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and examples thereof include benzyl. The aryl group is an aryl group which may have a substituent having 6 to 10 carbon atoms. For example, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4- Mention may be made of methanesulfonamidophenyl and 4-butanesulfonamidophenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and the number of heteroatoms constituting the ring and the type of element May be one or more, for example, oxazole ring, benzoxazole ring, 5-carboxybenzoxazole ring, thiazole ring, imidazole ring, pyridine ring, sulfolane ring, furan ring, thiophene ring, pyrazole ring, pyrrole ring , Chroman ring and coumarin ring.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The alkoxy group is an alkoxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methoxy, ethoxy, propoxy, and butoxy. The aryloxy group is an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenoxy and p-methoxyphenoxy. The alkylthio group is an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methylthio and ethylthio. The arylthio group is an arylthio group having 6 to 10 carbon atoms, and examples thereof include phenylthio. The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include acetoxy, propanoyloxy, pentanoyloxy, and octanoyloxy.

  The alkylamino group is an alkylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methylamino, dimethylamino, diethylamino, dibutylamino and octylamino. The amide group is an amide group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include acetamido, propanoylamino, pentanoylamino, octanoylamino, octanoylmethylamino, and benzamide. be able to. The sulfonamide group is a sulfonamide group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methanesulfonamide, ethanesulfonamide, propylsulfonamide, butanesulfonamide, and benzenesulfonamide. be able to. The alkoxycarbonylamino group is an alkoxycarbonylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methoxycarbonylamino and ethoxycarbonylamino. The alkoxysulfonylamino group is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methoxysulfonylamino and ethoxysulfonylamino.

  The sulfamoylamino group is a sulfamoylamino group which may have a substituent having 0 to 18 carbon atoms (preferably 0 to 8 carbon atoms), for example, methylsulfamoylamino, dimethylsulfamoylamino. And ethylsulfamoylamino, propylsulfamoylamino, and octylsulfamoylamino. The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include ureido, methylureido, N, N-dimethylureido, and octylureido. Can be mentioned. The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms). For example, thioureido, methylthioureido, N, N-dimethylthioureido, octylthio Ureido. The acyl group is an acyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include acetyl, benzoyl, and propanoyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methoxycarbonyl, ethoxycarbonyl, and octyloxycarbonyl.

  The carbamoyl group is a carbamoyl group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms). For example, carbamoyl, N, N-dimethylcarbamoyl, and N-ethylcarbamoyl are substituted. Can be mentioned. The alkyl or arylsulfonyl group is an alkyl or arylsulfonyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methanesulfonyl, ethanesulfonyl, and benzenesulfonyl. The alkylsulfinyl group is an alkylsulfinyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methanesulfinyl, ethanesulfinyl, and octanesulfinyl. The sulfamoyl group is a sulfamoyl group which may have a substituent having 0 to 18 carbon atoms (preferably 0 to 8 carbon atoms), for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, butylsulfamo Mention may be made of moyl, octylsulfamoyl and phenylsulfamoyl.

Z ¹ and Z ² are preferably a substituted or unsubstituted 3,3-dialkylindolenine nucleus and a 3,3-dialkylbenzoindolenine nucleus.

R ³⁰ and R ³¹ each independently represents an alkyl group. The alkyl group represented by R ³⁰ and R ³¹ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms). Are the same as those exemplified as the substituent of the nitrogen-containing heterocyclic ring, and the preferred range thereof is also the same. Preferably, it is an unsubstituted alkyl group or an alkyl group substituted with an aryl group, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, an amide group, a sulfonamide group, an alkoxycarbonyl group, a carboxyl group, or a sulfo group. Examples of these are methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, octyl, benzyl, 2-phenylethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-carboxyethyl, 3-carboxypropyl, 4 -Carboxybutyl, carboxymethyl, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2 Mention may be made of -hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, 2-acetoxyethyl, carbomethoxymethyl and 2-methanesulfonylaminoethyl.

The methine group represented by L ³ is an unsubstituted or substituted methine group, and the details of the substituent are the same as those described as the substituent of the nitrogen-containing heterocyclic ring, and the preferred range is also the same. is there. Moreover, when it has a substituent, an auxiliary color group and a 5-7 membered ring can also be formed.
L ³ is preferably an unsubstituted methine group.

  M1 represents a charge balanced counter ion. M1 may be a cation or an anion. Examples of the cation include alkali metal ions such as sodium ion, potassium ion and lithium ion, and organic ions such as tetraalkylammonium ion and pyridinium ion. The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluorine ion, chlorine ion, bromine ion, iodine ion), sulfonate ion (eg, methanesulfonate ion, trifluoromethane). Sulfonate ion, methyl sulfate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion) , Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, metal complex ion represented by the following formula:

And phosphate ions (for example, hexafluorophosphate ions, phosphate ions represented by the following formula:

Can be mentioned. m1 represents a number (0 or more, preferably a number of 0 to 4) necessary for balancing the electric charge, and is 0 when a salt is formed in the molecule. In the compound represented by the general formula (BI), two types may be bonded to each other on any carbon atom to form a bis-type structure.

The cyanine dyes represented by general formula (B-II), general formula (B-III), and general formula (B-IV) will be described in detail below. A preferable alkyl group represented by R ¹¹² , R ¹¹³ , R ²² , R ²³ , R ³² , R ³³ and R ³⁴ may have a chain or cyclic substituent having 1 to 20 carbon atoms. Good alkyl groups (eg methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, ter-butyl, methoxyethyl, hydroxyethyl, n-pentyl, isopentyl, cyclohexyl), more preferably An alkyl group having 1 to 6 carbon atoms, particularly preferably methyl, ethyl, n-propyl, n-butyl, or methoxyethyl.

A preferable aryl group represented by R ¹¹² , R ¹¹³ , R ²² , R ²³ and R ³² is an aryl group optionally having a substituent having 6 to 18 carbon atoms (eg, phenyl, 1-naphthyl). 2-naphthyl, 1-anthracenyl), more preferably phenyl, 1-naphthyl or 2-naphthyl, and particularly preferably phenyl.

Preferred as the aralkyl group represented by R ¹¹² , R ¹¹³ , R ²² , R ²³ , R ³² , R ³³ and R ³⁴ is an aralkyl group which may have a substituent having 7 to 18 carbon atoms ( For example, benzyl, phenethyl, anisyl), and benzyl is particularly preferable.

Preferred examples of the heterocyclic group represented by R ¹¹² , R ¹¹³ , R ²² , R ²³ , R ³² , R ³³ and R ^{34 have} a saturated or unsaturated substituent having 4 to 7 carbon atoms. The hetero atom contained therein is particularly preferably a nitrogen atom, an oxygen atom or a sulfur atom, such as 4-pyridyl, 2-pyridyl, 2-pyrazyl, 2-imidazolyl, 2-furyl, 2 -Thiophenyl, 2-benzoxazolyl, 2-benzothioxazolyl can be mentioned.

R ¹¹³ and R ²³ are preferably an aryl group or a heterocyclic group, more preferably an aryl group, and particularly preferably phenyl.

In the present invention, any of the alkyl group, aryl group, aralkyl group or heterocyclic group is used to represent a group which may have a substituent. Examples of the substituent that R ¹¹² , R ¹¹³ , R ²² , R ²³ , R ³² , R ^33, and R ³⁴ may have include those described below.
A linear or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl as a substituent other than an alkyl group), substituted or non-substituted having 6 to 18 carbon atoms Substituted aryl groups (eg phenyl, chlorophenyl, anisyl, toluyl, 2,4-di-t-amyl, 1-naphthyl), alkenyl groups (eg vinyl, 2-methylvinyl), alkynyl groups (eg ethynyl, 2-methylethynyl, 2-phenylethynyl), halogen atom (eg, F, Cl, Br, I), cyano group, hydroxyl group, carboxyl group, acyl group (eg, acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (Eg, methoxy, butoxy, cyclohexyloxy), aryloxy groups (eg, pheno Ci, 1-naphthoxy), alkylthio group (for example, methylthio, butylthio, benzylthio, 3-methoxypropylthio), arylthio group (for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (for example, methanesulfonyl, butanesulfonyl) An arylsulfonyl group (for example, benzenesulfonyl, paratoluenesulfonyl), a carbamoyl group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms. 10 acyloxy groups, alkoxycarbonyl groups having 2 to 10 carbon atoms, heterocyclic groups (for example, aromatic heterocycles such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidine ring, piperidine ring, morpholine ring, pyran Ring, thiopyran , Dioxane ring, an aliphatic hetero ring such as dithiolane rings).

  Examples of the substituent include alkyl groups having 1 to 6 carbon atoms (particularly methyl), aryl groups having 6 to 10 carbon atoms (particularly phenyl), alkoxy groups having 1 to 10 carbon atoms (particularly methoxy), and A halogen atom (especially a chlorine atom) is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

The methine groups represented by L ¹² , L ¹³ , L ²² , L ²³ , L ³² and L ³³ are each independently a methine group which may have a substituent. Examples of the substituent include those similar to those mentioned as examples of the substituent of the ^{R 112, R 113, R 22} , R 23, R 32, R 33 and ^{R 34.} The methine group represented by L ¹² , L ¹³ , L ²² , L ²³ , L ³² and L ³³ is an unsubstituted methine group or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl) as a substituent. , A methine group having a phenyl group, a chlorine atom, a carbamoyl group having 1 to 8 carbon atoms, an amide group having 1 to 8 carbon atoms, or an imide group having 2 to 8 carbon atoms, and particularly an unsubstituted methine group A methine group having methyl or phenyl as a substituent is preferable.

^{Each of the n2-} and n3-valent anions represented by ^Xn2- and ^Xn3- may be an inorganic anion or an organic anion. Examples of inorganic anions include halogen ions, chlorate ions, perchlorate ions, sulfate ions, hydrogen sulfate ions, phosphate ions, hydrogen phosphate ions, tungstophosphate ions, and the like. Examples of organic anions include carboxylate ions (eg acetate, trifluoroacetate, benzoate, oxalate, maleate, fumarate, terephthalate), sulfonate (eg methane) Sulfonic acid ion, trifluoromethanesulfonic acid ion, butane-1,4-disulfonic acid ion, cyclohexane-1,4-disulfonic acid ion, benzene-1,3-disulfonic acid ion, 3,3′-biphenyldisulfonic acid ion, Naphthalene-1,5-disulfonic acid ion, naphthalene-1,6-disulfonic acid ion, naphthalene-2,6-disulfonic acid ion, 1-methylnaphthalene-2,6-disulfonic acid ion, naphthalene-2,7-disulfone Acid ion, naphthalene-2,8-disulfonic acid ion 1-naphthol-3,6-disulfonic acid ion, 2-naphthol-3,6-disulfonic acid ion, 2,7-dihydroxy-3,6-disulfonic acid ion, 2-naphthol-6,8-disulfonic acid ion 1,8-dihydroxynaphthalene-3,6-disulfonic acid ion, 1,5-dihydroxynaphthalene-2,6-disulfonic acid ion, naphthalene-1,3,5-trisulfonic acid ion, naphthalene-1,3 6-trisulfonic acid ion, naphthalene-1,3,7-trisulfonic acid ion, 1-naphthol-3,6,8-trisulfonic acid ion, 2-naphthol-3,6,8-trisulfonic acid ion, Naphthalene-1,3,5,7-tetrasulfonate ion), polysulfate monoester (eg, propylene glycol-1,2-disulfate) , Polyvinyl alcohol polysulfate ion) and the like. Among them, a sulfonate ion is preferable, an aryl sulfonate ion is more preferable, and n2 or n3 is preferably 1 to 4 valence, more preferably 1 to 3. Yes, 2 is particularly preferable.

Heterocycles formed by Z ¹¹ , Z ²¹ and Z ³¹ include thiazoline ring, thiazole ring, benzothiazole ring, oxazoline ring, oxazole ring, benzoxazole ring, selenazoline ring, selenazole ring, benzoselenazole ring, 3, 3 -Dialkylindolenine ring (for example, 3,3-dimethylindolenine), 3,3-dialkylbenzoindolenine ring (for example, 3,3-dimethylbenzoindolenine), imidazoline ring, imidazole ring, benzimidazole ring, 2-pyridine Ring, 2-quinoline ring, 1-isoquinoline ring, 3-isoquinoline ring, imidazo [4,5-b] quinoxaline ring, oxadiazole ring, thiadiazole ring, tetrazole ring, pyrimidine ring, and the like are preferable. Is thiazoline ring, benzothiazo Ring, benzoxazole ring, 3,3-dialkylindolenine ring (for example, 3,3-dimethylindolenine), 3,3-dialkylbenzoindolenine ring (for example, 3,3-dimethylbenzoindolenine), benzimidazole ring , 2-pyridine ring, 2-quinoline ring, 1-isoquinoline ring, 3-isoquinoline ring, more preferably thiazoline ring, benzothiazole ring, benzoxazole ring, 3,3-dialkylindolenine ring (for example, 3,3 -Dimethylindolenine), 3,3-dialkylbenzoindolenine ring (for example, 3,3-dimethylbenzoindolenine), benzimidazole ring, particularly preferably thiazoline ring, benzothiazole ring, benzoxazole ring, benzimidazole ring Or 3,3-dimethylindolenine It is a ring.

The compound represented by the general formula (B-IV) may form a dimer, and is particularly preferably a dimer represented by the following general formula (B-V).
General formula (B-V)

In the formula, Z ³¹ , R ³² , L ³² and L ³³ have the same ^{meanings as} in the general formula (B-IV), L ⁴² and L ⁴³ have the same meanings as L ³² and L ³³ , respectively, and R ⁵⁰ represents a piperazine ring. Represents a substituent on a carbon atom or a condensed ring, r represents an integer of 0 to 8, (X ⁴ ) ^t- represents an organic or inorganic t-valent anion, and t represents an integer of 1 to 5. .

  Specific examples of the cyanine dye include cyanine dyes described in JP-A No. 2001-301333 and the following compounds, but are not limited thereto.

  The organic oxidant used for the cyanine dye and the cyanine dye is preferably paired in one molecule. Examples of compounds having a cyanine dye and an organic oxidizing agent in one molecule include the following compounds, but are not limited thereto.

  The oxonol dye represented by formula (CI) will be described in detail below.

  The general formula (CI) includes a plurality of tautomers due to differences in the notation of the localized positions of anions. In particular, any one of A, B, C, and D is -CO-E (E is a substituent) ), The negative charge is generally localized on the oxygen atom. For example, when D is -CO-E, the following general formula (C-I ') is common as the notation, and such a notation is also included in the general formula (CI).

The definitions of A, B, C, R, m ⁷¹ , n ⁷¹ , Y ^{t +} , and t in the general formula (CI ′) are the same as those in the general formula (CI).

Hereinafter, the oxonol dye represented by the general formula (CI) will be described. In general formula (C-I, A, B, C and D represent an electron-withdrawing group, and A and B or C and D may be linked to each other to form a ring. An electron-withdrawing group in which the sum of the Hammett σp values of A and B and the sum of the Hammett σp values of C and D are each 0.6 or more, R represents a substituent on the methine carbon, and m ⁷¹ is N represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of Rs may be the same as or different from each other, A ring may be formed, Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. A, B, C and D may be the same or different.

  Hammett's substituent constant σp value (hereinafter referred to as σp value) is described in, for example, Chem. Rev. 91, 165 (1991) and references cited therein, and those not described can be obtained by the method described in the same document. When A and B (C and D) are connected to form a ring, the σp value of A (C) means the σp value of the group -A-B-H (-C-D-H). , B (D) σp value means the σp value of the group -BAH (-DCH). In this case, both have different σp values because of different coupling directions.

  Preferable specific examples of the electron-withdrawing group represented by A, B, C and D include a cyano group, a nitro group, and an acyl group having 1 to 10 carbon atoms (eg, acetyl, propionyl, butyryl, pivaloyl, benzoyl). An alkoxycarbonyl group having 2 to 12 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, decyloxycarbonyl), an aryloxycarbonyl group having 7 to 11 carbon atoms (eg, phenoxy) Carbonyl), a carbamoyl group having 1 to 10 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl), an alkylsulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl), an aryl having 6 to 10 carbon atoms Sulfonyl group (eg, benzenesulfonyl) An alkoxysulfonyl group having 1 to 10 carbon atoms (eg, methoxysulfonyl), a sulfamoyl group having 1 to 10 carbon atoms (eg, ethylsulfamoyl, phenylsulfamoyl), an alkylsulfinyl group having 1 to 10 carbon atoms (Eg, methanesulfinyl, ethanesulfinyl), arylsulfinyl groups having 6 to 10 carbon atoms (eg, benzenesulfinyl), alkylsulfenyl groups having 1 to 10 carbon atoms (eg, methanesulfenyl, ethanesulfenyl), Arylsulfenyl group having 6 to 10 carbon atoms (eg, benzenesulfenyl), halogen atom, alkynyl group having 2 to 10 carbon atoms (eg, ethynyl), diacylamino group having 2 to 10 carbon atoms (eg, Diacetylamino), phosphoryl group, carboxyl group, 5-membered The Hajime Tamaki 6-membered (e.g., 2-benzothiazolyl, 2-benzoxazolyl, 3-pyridyl, 5-(IH) - tetrazolyl, 4-pyrimidyl) can be exemplified.

  In the general formula (CI), examples of the substituent on the methine carbon represented by R include those described below. A linear or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl), a substituted or unsubstituted aryl group having 6 to 18 carbon atoms (for example, phenyl) , Chlorophenyl, anisyl, toluyl, 2,4-di-t-amyl, 1-naphthyl), alkenyl group (for example, vinyl, 2-methylvinyl), alkynyl group (for example, ethynyl, 2-methylethynyl, 2-phenyl) Ethynyl), halogen atom (eg F, Cl, Br, I), cyano group, hydroxyl group, carboxyl group, acyl group (eg acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (eg methoxy, butoxy, cyclohexyl) Oxy), aryloxy groups (eg, phenoxy, 1-naphthoxy), alkylthio Group (e.g., methylthio, butylthio, benzylthio, 3-methoxypropylthio), an arylthio group (e.g., phenylthio, 4-chlorophenylthio)

An alkylsulfonyl group (for example, methanesulfonyl, butanesulfonyl), an arylsulfonyl group (for example, benzenesulfonyl, paratoluenesulfonyl), a carbamoyl group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, and the number of carbon atoms 2-12 imide groups, C2-C10 acyloxy groups, C2-C10 alkoxycarbonyl groups, heterocyclic groups (e.g., pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl and other heteroaromatics) Ring, pyrrolidine ring, piperidine ring, morpholine ring, pyran ring, thiopyran ring, dioxane ring, dithiolane ring and other aliphatic heterocycles).

  R is preferably a halogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 6 to 10 carbon atoms. An aryloxy group, a heterocyclic group having 3 to 10 carbon atoms, particularly a chlorine atom, an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, isopropyl), phenyl, 1 to 4 carbon atoms Alkoxy groups (eg, methoxy, ethoxy), phenoxy, and nitrogen-containing heterocyclic groups having 4 to 8 carbon atoms (eg, 4-pyridyl, benzoxazol-2-yl, benzothiazol-2-yl) are preferable.

n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1. When n ⁷¹ is an integer of 2 or more, a plurality of Rs may be the same as or different from each other, and may be connected to each other to form a ring. . At this time, the number of ring members is preferably 4 to 8, particularly preferably 5 or 6, and the constituent atoms of the ring are preferably carbon atoms, oxygen atoms or nitrogen atoms, and particularly preferably carbon atoms. n ⁷¹ is preferably 0.

  A, B, C, D and R may further have a substituent, and examples of the substituent include the examples of the monovalent substituent represented by R in the general formula (CI). The thing similar to what was mentioned in can be mentioned.

As the dye used for the optical disc, it is preferable that A and B or C and D are connected to form a ring from the viewpoint of thermal decomposability. m ⁷¹ represents an integer of 0 or 1, and is preferably 0.

Next, the cation represented by Y ^{t +} will be described in detail. Examples of the cation represented by Y ^{t +} include metal ions such as hydrogen ions or sodium ions, potassium ions, lithium ions, calcium ions, iron ions, and copper ions, metal complex ions, ammonium ions, pyridinium ions, and oxonium. Ions, sulfonium ions, phosphonium ions, selenonium ions, iodonium ions, and the like. Y ^{t +} is preferably a quaternary ammonium ion.

  Quaternary ammonium is generally a tertiary amine (eg, trimethylamine, triethylamine, tributylamine, triethanolamine, N-methylpyrrolidine, N-methylpiperidine, N, N-dimethylpiperazine, triethylenediamine, N, N, N ', N'-tetramethylethylenediamine, etc.) or nitrogen-containing heterocycle (pyridine ring, picoline ring, 2,2'-bipyridyl ring, 4,4'-bipyridyl ring, 1,10-phenanthroline ring, quinoline ring, oxazole ring , Thiazole ring, N-methylimidazole ring, pyrazine ring, tetrazole ring, etc.) can be obtained by alkylation (Menstokin reaction), alkenylation, alkynylation or arylation.

As the quaternary ammonium ion represented by Y ^{t +} , a quaternary ammonium ion composed of a nitrogen-containing heterocyclic ring is preferable, and a quaternary pyridinium ion is particularly preferable.

  t represents an integer of 1 to 10. Preferably it is 1-4. Particularly preferred is 2.

The cation represented by Y ^{t +} is more preferably a cation moiety represented by formula (I-2) described in JP-A No. 2000-052658. These compounds containing a cation moiety are usually a Mentostkin reaction of 2,2′-bipyridyl or 4,4′-bipyridyl with a halide having a desired substituent (see, for example, JP-A-61-148162) or It can be easily obtained by an arylation reaction according to the methods described in JP-A-51-16675 and JP-A-1-96171.
In addition, the cation part of the compound represented by the general formula (I-2) described in JP-A No. 2000-052658 corresponds to the pyridinium ion (quaternary pyridinium ion).

General formula (C-II), general formula (C-III), and general formula (C-IV) are demonstrated. C, D, R, m ⁷¹ , n ⁷¹ , Y ^{t +} , and t have the same meanings as those in formula (CI), and the preferred ranges are also the same. Y represents either —O— or —NR ¹ — or —CR ² R ³ —. Y is preferably —O— or —CR ² R ³ —, and more preferably —O—.

R ¹ , R ² , R ³ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a substituent. The substituents represented by R ¹ , R ² , R ³ , R ⁸ , and R ⁹ are not particularly limited, and examples thereof include the same substituents as those represented by R, and preferred ranges are also the same.

  Z represents a substituted or unsubstituted alkylene group. Preferred examples of the alkylene group include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group, more preferably a substituted or unsubstituted methylene group, or a substituted or unsubstituted group. A substituted ethylene group, more preferably a substituted or unsubstituted methylene group.

  x represents 1 or 2, and is preferably 2.

General formula (CV) and general formula (C-VI) will be described. C, D, R, m ⁷¹ , n ⁷¹ , Y ^{t +} , and t have the same meanings as those in formula (CI), and the preferred ranges are also the same. R ^{4 to} R ⁷ each independently represents a hydrogen atom or a substituent. Although it does not specifically limit as a substituent represented by R < ⁴ > -R < ⁷ >, The same thing as the substituent represented by said R is mentioned, A preferable range is also the same.

  G represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

Specific examples of the oxonol dye represented by formula (CI) used in the present invention include specific examples of the oxonol dyes described in the following patent documents. Some of the compounds are exemplified below.
[Patent Documents] JP-A 63-209995, JP-A 10-297103, JP-A 11-78106, JP-A 11-348420, JP-A 2000-52658, JP-A 2000-272241

  The pyridinium ion is preferably a compound represented by the general formula (D) or the general formula (E).

The general formula (D) or the general formula (E) will be described. The alkyl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is preferably a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably 1 carbon atom. To 8 substituted or unsubstituted linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, cyclohexyl, cyclopropyl and the like. Can be mentioned. Examples of the substituent of the alkyl group include a halogen atom (eg, F, Cl, Br, etc.), an alkoxy group having 1 to 18 carbon atoms, preferably an alkoxy group (eg, methoxy, ethoxy etc.) having 1 to 8 carbon atoms, 10 aryloxy (eg, phenoxy, p-methoxyphenoxy, etc.), alkylthio group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, etc.), arylthio group having 6 to 10 carbon atoms (eg, , Phenylthio, etc.), an acyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg, acetyl, propionyl, etc.), an acyloxy group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg, acetoxy) , Propionyloxy, etc.), an alkoxycarbonyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl) Alkenyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg vinyl), alkynyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (eg ethynyl etc.), Aryl groups having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), aryloxycarbonyl groups having 7 to 11 carbon atoms (eg, naphthoxycarbonyl, etc.), 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms Amino group (eg, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methyl Carbamoylamino, phenylcarbamoylamino, acetyl Amino, ethylcarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino, etc.), a carbamoyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, Ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.), sulfamoyl groups having 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms (eg, unsubstituted sulfamoyl, methyl Sulfamoyl, phenylsulfamoyl, etc.), cyano group, nitro group, carboxy group, hydroxyl group, heterocyclic group (eg, oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benzimi) Dazole, indolenine, pyridine, sulfolane, furan, thiophene, pyrazole, pyrrole, chroman, coumarin, etc.).

The alkenyl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is a substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Preferable examples include vinyl, allyl, isopropenyl, 1-propenyl, 1,3-butadienyl, cyclohexenyl and the like. The substituent for the alkenyl group has the same meaning as the substituents for the alkyl group other than the alkenyl group.

The alkynyl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is a substituted or unsubstituted linear, branched or cyclic alkynyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Preferable examples include ethynyl and 2-propynyl. The substituent for the alkynyl group has the same meaning as the substituent for the alkyl group other than the alkynyl group.

The aryl group represented by R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl and naphthyl. Can be mentioned. The substituent for the aryl group has the same definition as the substituent for the alkyl group, and examples of the substituent further include an alkyl group (eg, methyl, ethyl, etc.).

R ⁸¹ and R ⁸² may be connected to each other to form a ring. In the case of forming a ring, it is preferable that carbon atoms in R ⁸¹ and R ⁸² , carbon atoms and hetero atoms, or hetero atoms are bonded to each other. More preferably, they are carbon atoms, and particularly preferably, they are bonded by methylene groups.

R ⁸⁵ and R ⁸⁶ are preferably connected to each other to form a ring. The formed ring is preferably a 5-, 6- or 7-membered ring, more preferably a 6-membered ring. When a ring is formed, a ring is formed by bonding of carbon atoms in R ⁸⁵ and R ⁸⁶ , or a carbon atom and a hetero atom or hetero atoms, preferably, carbon atoms in R ⁸⁵ and R ⁸⁶ are bonded to each other. This is due to the combination of More preferably, it is a ring formed by bonding of methylene groups.

The substituent represented by R ⁸³ or R ⁸⁴ is, for example, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (for example, methyl, ethyl, etc.). Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl, acetoxyethyl, etc.), preferably 7 to 18 carbon atoms, Is a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl, carboxybenzyl, etc.), an alkenyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (for example, vinyl), 2 carbon atoms To 18, preferably an alkynyl group having 2 to 8 carbon atoms (eg, ethynyl, etc.) A substituted or unsubstituted aryl group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, etc.) A substituted or unsubstituted acyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (for example, acetyl, propionyl, butanoyl, chloroacetyl, etc.), 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms A substituted or unsubstituted sulfonyl group (for example, methanesulfonyl, p-toluenesulfonyl, etc.), an alkoxycarbonyl group having 2 to 18, preferably 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, etc.), carbon number An aryloxycarbonyl group having 7 to 18, preferably 7 to 12 carbon atoms (eg , Phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenylcarbonyl and the like), a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms (for example, methoxy, ethoxy, n-butoxy, Methoxyethoxy, etc.), substituted or unsubstituted aryloxy groups having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, etc.), 2 to 18 carbon atoms, preferably 2 carbon atoms To 8 substituted or unsubstituted acyloxy groups (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.), substituted or unsubstituted 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms Sulfonyloxy group (for example, methane Sulfonyloxy, etc.), a carbamoyloxy group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms (for example, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), a substitution having 0 to 18, preferably 0 to 8 carbon atoms, Unsubstituted amino group (for example, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonyl Amino, methylcarbamoylamino, phenylcarbamoylamino, ethylthiocarbamoylamino, methylsulfamoylamino, phenylsulfamoylamino, acetylamino, ethylcarbonylamino , Ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino, benzenesulfonylamino, etc.), a substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms ( For example, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.), substituted with 0 to 18 carbon atoms, preferably 0 to 8 carbon atoms Or an unsubstituted sulfamoyl group (for example, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a hydroxyl group, a nitro group, a cyano group , Carboxyl group, heterocyclic group and the like.

The substituent represented by R ⁸³ or R ⁸⁴ is preferably a hydrogen atom or an alkyl group. Particularly preferred is a hydrogen atom.

R ⁸³ and R ⁸⁴ may be connected to each other to form a carbocyclic or heterocyclic ring. Preferably, it is a carbocyclic ring, more preferably a condensed aromatic ring with a pyridine ring bonded to each of R ₃ and R ₄ .

  Examples of the quaternary ammonium salts represented by the general formula (D) and the general formula (E) include compounds described in JP-A-10-109475, JP-A-10-297103, and JP-A-2001-63211. However, it is not limited to these.

<Optical information recording medium>
The optical information recording medium of the present invention has an aspect [1]: a write-once recording layer containing a dye on a substrate having a thickness of 0.7 to 2 mm, a cover layer having a thickness of 0.01 to 0.5 mm, Information recording medium or embodiment [2] having the above in this order: a write-once recording layer containing a dye on a substrate having a thickness of 0.1 to 1.0 mm, and a protective substrate having a thickness of 0.1 to 1.0 mm And an optical information recording medium having the above in this order. In aspect [1], it is preferable that the track pitch of the pregroove formed on the substrate is 200 to 500 nm, the groove width is 25 to 250 nm, the groove depth is 5 to 150 nm, and the wobble amplitude is 10 to 50 nm. It is preferably 11 to 40 nm, more preferably 10 to 50 nm. In the aspect [2], the track pitch of the pregroove formed on the substrate is 200 to 600 nm, the groove width is 50 to 300 nm, the groove depth is 30 to 200 nm, and the wobble amplitude is 10 to 50 nm. It is preferably 11 to 40 nm, more preferably 10 to 50 nm.
The optical information recording medium of aspect [1] is an aspect having at least a substrate, a write-once recording layer, and a cover layer. First, members essential to these will be described in order.

[Substrate of Aspect [1]]
A pregroove (guide groove) having a shape in which the track pitch, the groove width (half width), the groove depth, and the wobble amplitude are all in the following ranges is formed on the substrate of the preferred embodiment [1]. It is essential. This pre-groove is provided to achieve a higher recording density than CD-R and DVD-R. For example, the optical information recording medium of the present invention is used as a medium corresponding to a blue-violet laser. It is suitable for use.

The track pitch of the pregroove is essential to be in the range of 200 to 500 nm, the upper limit value is preferably 420 nm or less, more preferably 370 nm or less, and further preferably 330 nm or less. The lower limit is preferably 210 nm or more, and more preferably 260 nm or more.
If the track pitch is less than 200 nm, it is difficult to accurately form the pregroove and a crosstalk problem may occur. If the track pitch exceeds 500 nm, the recording density may decrease.

The groove width (half width) of the pregroove is essential to be in the range of 25 to 250 nm, the upper limit is preferably 200 nm or less, more preferably 170 nm or less, and 150 nm or less. Further preferred. Further, the lower limit is preferably 50 nm or more, more preferably 80 nm or more, and further preferably 100 nm or more.
If the groove width of the pregroove is less than 25 nm, the groove may not be sufficiently transferred at the time of molding, or the recording error rate may increase. If it exceeds 250 nm, the pits formed during recording will spread, It may cause crosstalk or a sufficient degree of modulation may not be obtained.

The groove depth of the pregroove is essential to be in the range of 5 to 150 nm, the upper limit is preferably 100 nm or less, more preferably 70 nm or less, and further preferably 50 nm or less. Further, the lower limit is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 28 nm or more.
If the groove depth of the pregroove is less than 5 nm, a sufficient recording modulation degree may not be obtained, and if it exceeds 150 nm, the reflectivity may be significantly lowered.

Further, the upper limit of the groove inclination angle of the pregroove is preferably 80 ° or less, more preferably 75 ° or less, and particularly preferably 70 ° or less. Further, the lower limit value is preferably 20 ° or more, more preferably 30 ° or more, and further preferably 40 ° or more.
If the groove inclination angle of the pregroove is less than 20 °, a sufficient tracking error signal amplitude may not be obtained, and if it exceeds 80 °, molding becomes difficult.

As the substrate used in the present invention, various materials used as substrate materials for conventional optical information recording media can be arbitrarily selected and used.
Specifically, glass; acrylic resin such as polycarbonate and polymethyl methacrylate; vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer; epoxy resin; amorphous polyolefin; polyester; metal such as aluminum; These may be used together if desired.
Among the above materials, thermoplastic resins such as amorphous polyolefin and polycarbonate are preferable, and polycarbonate is particularly preferable from the viewpoints of moisture resistance, dimensional stability, and low price.
When these resins are used, the substrate can be manufactured by injection molding.
Further, the thickness of the substrate needs to be in the range of 0.7 to 2 mm, preferably in the range of 0.9 to 1.6 mm, and more preferably 1.0 to 1.3 mm. .

In addition, it is preferable to form an undercoat layer on the substrate surface on the side where a light reflecting layer described later is provided for the purpose of improving the flatness and the adhesive force.
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, and chloro. Polymer materials such as sulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc .; silane coupling Surface modifiers such as agents;
The undercoat layer is formed by dissolving or dispersing the above materials 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. The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, and preferably in the range of 0.01 to 10 μm.

[Write-once recording layer of embodiment [1]]
In the write-once recording layer of the preferred embodiment [1], a dye is dissolved in a suitable solvent together with a binder and the like to prepare a coating solution, and then this coating solution is coated on a substrate or a light reflecting layer described later. After forming a coating film, it is formed by drying. Here, the write-once recording layer may be a single layer or a multilayer. In the case of a multilayer structure, the step of applying the coating liquid is performed a plurality of times.
The concentration of the dye in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, most preferably. It is the range of 0.5-3 mass%.

Examples of the solvent of the coating solution include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; dimethylformamide and the like Amides; Hydrocarbons such as methylcyclohexane; Ethers such as tetrahydrofuran, ethyl ether, dioxane; Alcohols such as ethanol, n-propanol, isopropanol, n-butanol diacetone alcohol; 2,2,3,3-tetrafluoropropanol, etc. Fluorinated solvents; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether; That.
The above solvents can be used alone or in combination of two or more in consideration of the solubility of the dye used. In the coating solution, various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added according to the purpose.

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.
At the time of application, the temperature of the coating solution is preferably in the range of 23 to 50 ° C, more preferably in the range of 24 to 40 ° C, and particularly preferably in the range of 23 to 50 ° C.

The thickness of the write-once recording layer formed in this way is preferably 300 nm or less, more preferably 250 nm or less, and more preferably 200 nm or less on the groove (convex portion in the substrate). More preferably, it is particularly preferably 180 nm or less. The lower limit is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more, and particularly preferably 90 nm or more.
Further, the thickness of the write-once recording layer is preferably 400 nm or less, more preferably 300 nm or less, and further preferably 250 nm or less on the land (the concave portion in the substrate). The lower limit is preferably 70 nm or more, more preferably 90 nm or more, and further preferably 110 nm or more.
Further, the ratio of the thickness of the write-once recording layer on the groove / the thickness of the write-once recording layer on the land is preferably 0.4 or more, more preferably 0.5 or more, and 6 or more is more preferable, and 0.7 or more is particularly preferable. The upper limit is preferably less than 1, more preferably 0.9 or less, still more preferably 0.85 or less, and particularly preferably 0.8 or less.

  When the coating solution contains a binder, examples of the binder include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin, and rubber; hydrocarbon resins such as polyethylene, polypropylene, polystyrene, and polyisobutylene. , Polyvinyl chloride, polyvinylidene chloride, vinyl resins such as polyvinyl chloride / polyvinyl acetate copolymer, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral And synthetic organic polymers such as resins, rubber derivatives, and initial condensates of thermosetting resins such as phenol / formaldehyde resins. When a binder is used in combination as a material for the write-once recording layer, the amount of binder used is generally in the range of 0.01 to 50 times (mass ratio) with respect to the dye, preferably 0.1. It exists in the range of double amount-5 times amount (mass ratio).

In addition, the write-once recording layer can contain various anti-fading agents in order to improve the light resistance of the write-once recording layer. As the anti-fading agent, a singlet oxygen quencher is generally used. In the present invention, further improvement in light resistance can be expected by mixing the singlet oxygen quencher. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used.
Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19587, and 60-35054. 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, JP-A-60-47069, JP-A-63-209995, JP-A-4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent No. 350399, and Japan Examples include those described in Chemical Society Journal, October 1992, page 1141.
The amount of the antifading agent such as the singlet oxygen quencher used is usually in the range of 0.1 to 50% by weight, preferably in the range of 0.5 to 45% by weight, based on the amount of the dye. Preferably, it is the range of 3-40 mass%, Most preferably, it is the range of 5-25 mass%.

[Cover layer of embodiment [1]]
The cover layer of the preferred embodiment [1] is bonded to the write-once recording layer described above or a barrier layer described later via an adhesive or an adhesive material.
The cover layer used in the present invention is not particularly limited as long as it is a transparent material film; however, an acrylic resin such as polycarbonate and polymethyl methacrylate; a vinyl chloride resin such as polyvinyl chloride and a vinyl chloride copolymer; It is preferable to use epoxy resin; amorphous polyolefin; polyester; cellulose triacetate and the like. Among them, it is more preferable to use polycarbonate or cellulose triacetate.
Note that “transparent” means that the transmittance is 80% or more with respect to light used for recording and reproduction.

Further, the cover layer may contain various additives as long as the effects of the present invention are not hindered. For example, a pigment for cutting light of 500 nm or more may be contained.
Further, as the surface physical properties of the cover layer, it is preferable that both the two-dimensional roughness parameter and the three-dimensional roughness parameter have a surface roughness of 5 nm or less.
Further, from the viewpoint of the concentration of light used for recording and reproduction, the birefringence of the cover layer is preferably 10 nm or less.

The thickness of the cover layer is appropriately defined by the wavelength and NA of the laser light irradiated for recording and reproduction. In the present invention, the thickness is in the range of 0.01 to 0.5 mm, and 0 More preferably, it is in the range of 0.05 to 0.12 mm.
The total thickness of the cover layer and the layer made of an adhesive or a pressure-sensitive adhesive is preferably 0.09 to 0.11 mm, and more preferably 0.095 to 0.105 mm.
The light incident surface of the cover layer may be provided with a protective layer (hard coat layer) for preventing the light incident surface from being damaged when the optical information recording medium is manufactured.

For example, a UV curable resin, an EB curable resin, a thermosetting resin, or the like is preferably used as the adhesive used to bond the cover layer, and it is particularly preferable to use a UV curable resin.
When a UV curable resin is used as an adhesive, the UV curable resin may be used as it is or dissolved in an appropriate solvent such as methyl ethyl ketone or ethyl acetate to prepare a coating solution, which may be supplied from the dispenser to the barrier layer surface. . Further, in order to prevent warpage of the produced optical information recording medium, it is preferable that the UV curable resin constituting the adhesive layer has a small curing shrinkage rate. Examples of such UV curable resins include UV curable resins such as “SD-640” manufactured by Dainippon Ink and Chemicals, Inc.

The adhesive is applied, for example, on a surface to be bonded composed of a barrier layer, and after a cover layer is placed thereon, the adhesive is applied by spin coating to the surface to be bonded and the cover layer. It is preferable that the film is cured after being spread so as to be uniform.
The thickness of the adhesive layer made of such an adhesive is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.5 to 50 μm, and still more preferably in the range of 10 to 30 μm.

  As the pressure-sensitive adhesive used for laminating the cover layer, acrylic, rubber-based, and silicon-based pressure-sensitive adhesives can be used. From the viewpoint of transparency and durability, acrylic pressure-sensitive adhesive is used. preferable. As such an acrylic pressure-sensitive adhesive, 2-ethylhexyl acrylate, n-butyl acrylate and the like are the main components, and in order to improve cohesion, short-chain alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, and methyl methacrylate are used. And acrylic acid, methacrylic acid, acrylamide derivatives, maleic acid, hydroxylethyl acrylate, glycidyl acrylate, and the like, which can be crosslinking points with the crosslinking agent, are preferably used. The glass transition temperature (Tg) and the crosslinking density can be changed by appropriately adjusting the mixing ratio and type of the main component, the short chain component, and the component for adding a crosslinking point.

  As a crosslinking agent used together with the said adhesive, an isocyanate type crosslinking agent is mentioned, for example. Such isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine isocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, and the like. Isocyanates, products of these isocyanates with polyalcohols, and polyisocyanates formed by condensation of isocyanates can be used. Commercially available products of these isocyanates include Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate HTL manufactured by Nippon Polyurethane; Takenate D-102 and Takenate D-110N manufactured by Takeda Pharmaceutical Co., Ltd. , Takenate D-200, Takenate D-202; Death Module L, Death Module IL, Death Module N, Death Module HL;

The pressure-sensitive adhesive may be uniformly applied on the surface to be bonded made of the barrier layer, and may be cured after placing the cover layer thereon, or in advance on one side of the cover layer, A predetermined amount may be uniformly applied to form an adhesive coating film, the coating film may be bonded to the surface to be bonded, and then cured.
Moreover, you may use the commercially available adhesive film in which the adhesive layer was previously provided for the cover layer.
The thickness of the pressure-sensitive adhesive layer made of such a pressure-sensitive adhesive is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.5 to 50 μm, and still more preferably in the range of 10 to 30 μm.

[Other Layers in Aspect [1]]
The optical information recording medium of the preferred embodiment [1] may have other arbitrary layers in addition to the above essential layers as long as the effects of the present invention are not impaired. As such other optional layers, for example, a label layer having a desired image formed on the back surface of the substrate (the back surface with respect to the write-once recording layer forming surface), or between the substrate and the write-once recording layer is provided. And a barrier layer (described later) provided between the write-once recording layer and the cover layer, an interface layer provided between the light reflective layer and the write-once recording layer, and the like. Here, the label layer is formed using an ultraviolet curable resin, a thermosetting resin, a heat drying resin, or the like.
These essential and optional layers may be a single layer or may have a multilayer structure.

[Light Reflecting Layer in Aspect [1]]
In the optical information recording medium of the preferred embodiment [1], a light reflecting layer is formed between the substrate and the write-once recording layer in order to increase the reflectivity for laser light and to give the function of improving the recording / reproducing characteristics. It is preferable to do.
The light reflecting layer can be formed on the substrate by vacuum-depositing, sputtering, or ion plating a light-reflecting material having a high reflectance with respect to laser light.
The thickness of the light reflecting layer is generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.
The reflectance is preferably 70% or more.

  As a light reflective material having a high reflectance, Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, 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 other metals and semi-metals or stainless steel. These light reflecting materials may be used alone or in combination of two or more or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred is Au, Ag, Al or an alloy thereof, and most preferred is Au, Ag or an alloy thereof.

[Step of Forming Barrier Layer (Intermediate Layer) in Aspect [1]]
In the optical information recording medium of the preferred embodiment [1], it is preferable to form a barrier layer between the write-once recording layer and the cover layer.
The barrier layer is provided for improving the storage stability of the write-once recording layer, improving the adhesion between the write-once recording layer and the cover layer, adjusting the reflectance, adjusting the thermal conductivity, and the like.
The material used for the barrier layer is not particularly limited as long as it is a material that transmits light used for recording and reproduction, and can express the above functions. Is a material with low gas and moisture permeability and is preferably a dielectric.
Specifically, a material made of nitride, oxide, carbide, or sulfide such as Zn, Si, Ti, Te, Sn, Mo, or Ge is preferable. ZnS, MoO ₂ , GeO ₂ , TeO, SiO ₂ , TiO ₂ , ZuO, ZnS—SiO ₂ , SnO ₂ and ZnO—Ga ₂ O ₃ are preferable, and ZnS—SiO ₂ , SnO ₂ and ZnO—Ga ₂ O ₃ are more preferable.

The barrier layer can be formed by a vacuum film forming method such as vacuum deposition, DC sputtering, RF sputtering, or ion plating. Among these, it is more preferable to use sputtering, and it is more preferable to use RF sputtering.
The thickness of the barrier layer in the present invention is preferably in the range of 1 to 200 nm, more preferably in the range of 2 to 100 nm, and still more preferably in the range of 3 to 50 nm.

Next, the optical information recording medium of the preferred embodiment [2] will be described.
Here, the optical information recording medium of the mode [2] is an optical information recording medium having a laminated type layer structure, and a typical layer structure is as follows.
(1) The first layer configuration is a configuration in which a write-once recording layer, a light reflection layer, and an adhesive layer are sequentially formed on a substrate, and a protective substrate is provided on the adhesive layer.
(2) The second layer configuration is a configuration in which a write-once recording layer, a light reflection layer, a protective layer, and an adhesive layer are sequentially formed on a substrate, and a protective substrate is provided on the adhesive layer.
(3) The third layer configuration is a configuration in which a write-once recording layer, a light reflection layer, a protective layer, an adhesive layer, and a protective layer are sequentially formed on a substrate, and a protective substrate is provided on the protective layer.
(4) In the fourth layer configuration, a write-once recording layer, a light reflecting layer, a protective layer, an adhesive layer, a protective layer, and a light reflecting layer are sequentially formed on a substrate, and a protective substrate is provided on the light reflecting layer. It is a configuration.
(5) The fifth layer configuration is a configuration in which a write-once recording layer, a light reflecting layer, an adhesive layer, and a light reflecting layer are sequentially formed on a substrate, and a protective substrate is provided on the light reflecting layer.
Note that the layer configurations (1) to (5) are merely examples, and the layer configuration is not limited to the order described above, and a part of the layer configuration may be replaced or a part of the layer configuration may be omitted. The write-once recording layer may also be formed on the protective substrate side. In this case, an optical information recording medium capable of recording and reproducing from both sides is obtained. Furthermore, each layer may be composed of one layer or a plurality of layers.
As an example of the optical information recording medium of the present invention, a recording medium having a write-once recording layer, a light reflecting layer, an adhesive layer, and a protective substrate in this order will be described below.

[Substrate [2]]
In the preferred embodiment [2], a pregroove (guide groove) having a shape in which all of the track pitch, groove width (half width), groove depth, and wobble amplitude are in the following ranges is formed. It is essential. This pre-groove is provided to achieve a higher recording density than CD-R and DVD-R. For example, the optical information recording medium of the present invention is used as a medium corresponding to a blue-violet laser. It is suitable for use.

The track pitch of the pregroove is essential to be in the range of 200 to 500 nm, and the upper limit is preferably 450 nm or less, and more preferably 430 nm or less. The lower limit is preferably 300 nm or more, more preferably 330 nm or more, and still more preferably 370 nm or more.
If the track pitch is less than 200 nm, it is difficult to accurately form the pregroove and a crosstalk problem may occur. If the track pitch exceeds 500 nm, the recording density may decrease.

  The groove width (half width) of the pregroove is in the range of 50 to 300 nm, the upper limit is preferably 250 nm or less, more preferably 200 nm or less, and 180 nm or less. Further preferred. Further, the lower limit value is preferably 100 nm or more, more preferably 120 nm or more, and further preferably 140 nm or more. If the groove width of the pregroove is less than 50 nm, the groove may not be sufficiently transferred at the time of molding or the recording error rate may be high. If it exceeds 300 nm, the pits formed at the time of recording spread. It may cause crosstalk or a sufficient degree of modulation may not be obtained.

The groove depth of the pregroove is essential to be in the range of 30 to 200 nm, the upper limit is preferably 170 nm or less, more preferably 140 nm or less, and further preferably 120 nm or less. The lower limit is preferably 40 nm or more, more preferably 50 nm or more, and further preferably 60 nm or more.
When the groove depth of the pregroove is less than 30 nm, a sufficient recording modulation degree may not be obtained, and when it exceeds 200 nm, the reflectivity may be significantly lowered.

As the substrate used in the preferred embodiment [2], various materials used as substrate materials for conventional optical information recording media can be arbitrarily selected and used. Specific examples and preferred examples are shown in the embodiment [1]. ] Is the same as the substrate.
Further, the thickness of the substrate needs to be in the range of 0.1 to 1.0 mm, preferably in the range of 0.2 to 0.8 mm, and in the range of 0.3 to 0.7 mm. It is more preferable.

  In addition, it is preferable to form an undercoat layer on the substrate surface on the side on which the write-once recording layer described later is provided for the purpose of improving flatness and adhesion, and the material of the undercoat layer and the coating method Specific examples and preferred examples of the layer thickness are the same as those of the undercoat layer of the embodiment [1].

[Write-once recording layer of embodiment [2]]
The detailed description of the write-once recording layer of the preferred embodiment [2] is the same as that of the write-once recording layer of the embodiment [1].

[Light Reflecting Layer of Aspect [2]]
In a preferred embodiment [2], a light reflecting layer may be formed on the write-once recording layer in order to increase the reflectance with respect to the laser beam or to give the function of improving the recording / reproducing characteristics. Details regarding the light reflecting layer of aspect [2] are the same as those of the light reflecting layer of aspect [1].

[Adhesive layer of embodiment [2]]
The adhesive layer in the preferred embodiment [2] is an arbitrary layer formed in order to improve the adhesion between the light reflecting layer and the protective substrate.
As a material constituting the adhesive layer, a photo-curing resin is preferable, and in particular, a material having a small curing shrinkage rate is preferable in order to prevent the disk from warping. Examples of such a photocurable resin include UV curable resins (UV curable adhesives) such as “SD-640” and “SD-347” manufactured by Dainippon Ink, Inc. Further, the thickness of the adhesive layer is preferably in the range of 1 to 1000 μm in order to give elasticity.

[Protective substrate of embodiment [2]]
The protective substrate (dummy substrate) in the preferred embodiment [2] can be made of the same material and the same shape as those described above. The thickness of the protective substrate requires a thickness in the range of 0.1 to 1.0 mm, preferably in the range of 0.2 to 0.8 mm, and in the range of 0.3 to 0.7 mm. It is more preferable that

[Protective layer of embodiment [2]]
In the optical information recording medium of the preferred embodiment [2], a protective layer may be provided for the purpose of physically and chemically protecting the light reflecting layer and the write-once recording layer depending on the layer structure.
Examples of materials used for the protective layer include inorganic substances such as ZnS, ZnS—SiO ₂ , SiO, SiO ₂ , MgF ₂ , SnO ₂ , and Si ₃ N ₄ , thermoplastic resins, thermosetting resins, and UV curable materials. Organic substances such as resins can be mentioned.
The protective layer can be formed, for example, by bonding a film obtained by plastic extrusion onto the light reflecting layer via an adhesive. Moreover, you may provide by methods, such as vacuum evaporation, sputtering, and application | coating.

Further, when a thermoplastic resin or a thermosetting resin is used as the protective layer, it is also formed by dissolving these in an appropriate solvent to prepare a coating solution, and then applying and drying the coating solution. be able to. 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, and then applying the coating solution and curing it by irradiation 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 μm to 1 mm.

[Other layers of embodiment [2]]
The optical information recording medium of the preferred embodiment [2] may have other arbitrary layers in addition to the above-mentioned layers as long as the effects of the present invention are not impaired. The detailed description of such other optional layers is the same as that of the other layers of the embodiment [1].

<Optical information recording method>
The optical information recording method of the present invention is performed, for example, as follows using the optical information recording medium of the preferred embodiment [1] or [2]. First, recording light such as semiconductor laser light is irradiated from the substrate side or the protective layer side while rotating the optical information recording medium at a constant linear velocity (0.5 to 10 m / sec) or a constant angular velocity. By this light irradiation, the recording layer absorbs the light and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) and changing its optical characteristics, thereby recording information. It is thought that it is done. In the present invention, semiconductor laser light having an oscillation wavelength in the range of 390 to 450 nm is used as recording light. As a preferred light source, a blue-violet semiconductor laser beam having an oscillation wavelength in the range of 390 to 415 nm, and a blue-violet SHG having a central oscillation wavelength of 425 nm obtained by halving an infrared semiconductor laser beam having a central oscillation wavelength of 850 nm using an optical waveguide device. A laser beam can be mentioned. In particular, it is preferable to use a blue-violet semiconductor laser beam having an oscillation wavelength in the range of 390 to 415 nm in terms of recording density. The information recorded as described above is reproduced by irradiating a semiconductor laser beam from the substrate side or the protective layer side while rotating the optical information recording medium at the same constant linear velocity as above and detecting the reflected light. Can be performed.

[Example]
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to a following example.

An example of the synthesis method of the cyanine dye of the present invention is shown below.
[Synthesis of Compound (I-1)]

2 g of compound (111) and 146 mg of piperazine were heated to reflux in 10 ml of acetonitrile for 6 hours. It returned to room temperature, the produced | generated deposit was filtered, and 1.16g of compounds (112) were obtained by wash | cleaning with acetonitrile.
Next, 0.5 g of the compound (112) and 0.27 g of disodium 2,7-dihydroxynaphthalene-3,6-disulfonate were heated to reflux in 10 ml of methanol and 10 ml of water for 1.5 hours. It returned to room temperature, the produced | generated deposit was filtered, and 0.5g of compounds (I-1) were obtained by wash | cleaning with methanol. The structure was confirmed by NMR. ¹ HNMR (DMSO-d6): d = 0.9 (t, 6H), 1.4 (t, 10H), 1.7 (m, 4H), 3.8 (br, 8H), 4.5 ( m, 8H), 5.4 (br, 2H), 6.9 (s, 2H), 7.8 (d, 2H), 7.9 (s, 2H), 8.3 (d, 4H), 10.4 (s, 2H)

[Synthesis of Compound (I-13)]

0.1 g of the compound (114) and 78 mg of the compound (115) were reacted in 10 ml of methanol and 10 ml of water for 1.5 hours at room temperature. The produced precipitate was filtered and washed with methanol to obtain 0.1 g of Compound (I-13). The structure was confirmed by NMR. ¹ HNMR (DMSO-d6): d = 0.9 (t, 6H), 1.3 (m, 14H), 1.7 (br, 4H), 3.8 (br, 8H), 4.1 ( br, 4H), 4.4-4.5 (m, 12H), 5.4 (d, 2H), 6.4 (br, 2H), 7.8 (d, 2H), 8.2 (d , 4H)

An example of a method for synthesizing the oxonol dye of the present invention is shown below.
[Synthesis of Compound (II-6)]

17.3 g of compound (116) and 8.78 g of compound (117) were dissolved in 200 ml of acetonitrile, 5.31 ml of acetic anhydride was added dropwise with stirring, and 7.91 ml of triethylamine was further added dropwise. The mixture was reacted at 80 ° C. for 1 hour, distilled off the solvent, and purified by silica gel column chromatography to obtain 19.6 g of compound (II-0).
0.67 g of compound (II-0) was dissolved in 10 ml of methanol, 0.37 g of compound (119) was added, and the resulting crystals were filtered to obtain 0.66 g of compound (II-6). The structure was confirmed by NMR.
¹ HNMR (DMSO-d6): d = 1.3 (m, 1H), 1.5 (m, 3H), 1.75 (m, 6H), 3.1 (d, 6H) 7.2-8 0.0 (m, 8H), 8.05 (s, 1H), 9.00 (d, 2H), 9.65 (d, 2H), 10.71 (s, 1H).

<Manufacture of optical information recording medium 1>
(Production of substrate)
Thickness 1.1 mm, outer diameter 120 mm, inner diameter 15 mm, spiral pre-groove (track pitch: 320 nm, groove width: on-groove width 120 nm, groove depth: 35 nm, groove inclination angle: 65 °, wobble amplitude: 20 nm) An injection-molded substrate made of a polycarbonate resin was prepared. Mastering of the stamper used at the time of injection molding was performed using laser cutting (351 nm).

(Formation of light reflection layer)
APC light reflecting layer (Ag: 98.1 mass%, Pd: 0.9 mass) as a vacuum film-forming layer having a film thickness of 100 nm by DC sputtering in an Ar atmosphere using a Cube manufactured by Unaxis Co. %, Cu: 1.0 mass%). The film thickness of the light reflecting layer was adjusted by the sputtering time.

(Formation of write-once recording layer)
A recording layer is formed by dissolving the dye compound according to the present invention or a combination of the dye compound and a nickel complex a represented by the following formula (see Table 1) in a solvent of 2,2,3,3-tetrafluoropropanol. A coating solution was prepared. The amount of anti-fading agent added was 10% by mass with respect to the pigment. The density | concentration of the obtained coating liquid was 2.5 mass%. And the prepared pigment | dye containing coating liquid was apply | coated on the conditions of 23 degreeC and 50% RH, changing the rotation speed to 300-4000 rpm with a spin coat method on the light reflection layer. Then, it was stored at 23 ° C. and 50% RH for 1 hour to form a write-once recording layer (thickness on the groove 120 nm, thickness on the land 170 nm).

  Nickel complex a

  After the write-once recording layer was formed, annealing treatment was performed in a clean oven. The annealing treatment was performed by supporting the substrate on a vertical stack pole while leaving a gap with a spacer, and holding at 80 ° C. for 1 hour.

(Formation of barrier layer)
Then, on the write-once recording layer, using Cubes manufactured by Unaxis, and made of ZnO—Ga ₂ O ₃ (ZnO: Ga ₂ O ₃ = 7: 3 (mass ratio)) by RF sputtering in an Ar atmosphere. A barrier layer having a thickness of 5 nm was formed.

(Covering the cover layer)
As the cover layer, a polycarbonate film (Teijin Pure Ace, thickness: 80 μm) having an inner diameter of 15 mm and an outer diameter of 120 mm and coated with an adhesive on one side, the thickness of the adhesive layer and the polycarbonate film is used. The total thickness was set to 100 μm.
Then, the cover layer was placed on the barrier layer so that the barrier layer and the pressure-sensitive adhesive layer were in contact with each other, and the cover layer was pressed and pressed with a pressing member.
Thereby, the optical information recording media of Examples 1 to 3 and Comparative Example 1 were produced.

<Evaluation of optical information recording medium 1>
(1) C / N (carrier-to-noise ratio) evaluation Using a recording / reproduction evaluation machine (manufactured by Pulstec Inc .: DDU1000) loaded with a 403 nm laser and NA 0.85 pickup, the produced optical information recording medium was used with a clock frequency of 66 MHz, A 0.16 μm signal (2T) was recorded and reproduced at a linear velocity of 5.28 m / s, and C / N (after recording) was measured with a spectrum analyzer (Pulstech MSG2). Moreover, Xe lamp (Merry-go-round type light resistance tester manufactured by Eagle Engineering, Cell Tester III-500W type, with heat ray reflection filter) was irradiated for 12 hours (h), and the subsequent pit observation was performed. This evaluation was performed using the optical information recording method of the present invention, and recording was performed on a groove. The recording power was 5 mW and the reproducing power was 0.3 mW. The results are shown in Table 1. Here, when the C / N (after recording) is 25 dB or more, the reproduction signal intensity is sufficient, which is practically preferable.

  As shown in the results of Table 1 above, in the case of the sample of the oxonol dye compound according to the present invention, all of the samples are superior in recording / reproducing characteristics as compared with the sample combined with the nickel complex a which is a conventional anti-fading agent. There is little deterioration in performance after Xe lamp irradiation, and light resistance is improved.

  Furthermore, the produced optical information recording medium was stored for 24 hours in an environment of a temperature of 60 ° C. and a relative humidity of 80%, and the same measurement was performed (heating and humidification experiments). As a result, pits could not be read for Comparative Example 1. On the other hand, in Examples 1 to 3, pits could be read.

  In the case of the sample of the oxonol dye according to the present invention (Examples 1 to 3) as shown in Table 1 and the results of the heating and humidification experiments, the oxonol dye according to the present invention and the conventional anti-fading agent are used. As compared with the sample combined with the nickel complex a, the recording / reproduction characteristics, light resistance, and storage stability under high temperature and high humidity are all excellent.

  Also in the case where the production of the optical information recording medium was carried out using the compounds (II-9), (II-10), (II-13), (II-14) and (II-15), Examples 1 to It was confirmed that the recording layer can be formed in the same manner as in No. 3, the recording / reproducing characteristics are excellent, the performance is not deteriorated after irradiation with the Xe lamp, and the storage stability under high temperature and high humidity is also good.

  From the results of Table 1 above, in the case of a sample in which the cyanine dye according to the present invention and the organic oxidant represented by the general formula (A) are combined, the deterioration amount of the dye is remarkable even after irradiation with the Xe lamp. It can be seen that it is suppressed. In particular, when the cyanine dye or oxonol dye and the organic oxidizing agent are used, the difference (b−a) between the oxidation potential of the cyanine dye or oxonol dye and the reduction potential of the organic oxidizing agent is in the range of 0 <b−a <1.6. In the case of the sample combined as described in (1), it can be seen that the amount of residual dye is also large, and therefore it has good light resistance.

Claims (11)

  An optical information recording medium having a recording layer capable of recording information by irradiation with a laser beam of 440 nm or less on a substrate, wherein the recording layer contains a methine dye and an organic oxidizing agent, .   The substrate is a transparent disk-like substrate on which a pregroove having a track pitch of 0.2 to 0.5 μm is formed, and the recording layer is provided on the surface on which the pregroove is provided. The heat mode type information recording medium according to claim 1.   3. The information recording medium according to claim 1, wherein the oxidation potential b volt of the methine dye is in a range of 0.5 <b <1.2.   The information recording medium according to claim 1, further comprising a recording layer containing the organic oxidant having a reduction potential nobler than −0.4 volts.   The information recording medium according to claim 1, wherein the organic oxidant is a quaternary ammonium ion or a pyridinium ion. 6. The information recording medium according to claim 1, wherein the organic oxidant is a compound represented by the following general formula (D) or (E).

[Wherein R ⁸¹ and R ⁸² represent an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R ⁸³ and R ⁸⁴ represent a substituent (including a substituent atom). R ⁸⁵ and R ⁸⁶ represent an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ or R ⁸⁵ and R ⁸⁶ may be connected to each other to form a ring. p and q represent an integer of 0 to 4, and when p is 2 or more, R ⁸³ may be the same or different from each other, and when q is 2 or more, R ⁸⁴ may be the same or different from each other. ] The information recording medium according to claim 1, wherein the methine dye is an oxonol dye represented by the general formula (CI).
General formula (CI)

[Wherein, A, B, C and D represent an electron-withdrawing group, and A and B or C and D may be linked to each other to form a ring. This is an electron-withdrawing group in which the sum of the Hammett σp values and the sum of the Hammett σp values of C and D are each 0.6 or more. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. ] The methine dye is an oxonol dye represented by General Formula (C-II), General Formula (C-III), or General Formula (C-IV). The information recording medium described.
Formula (C-II)

Formula (C-III)

Formula (C-IV)

[Wherein, C and D represent an electron-withdrawing group, which may be linked to each other to form a ring, and when not linked to each other, the sum of the Hammett σp values of C and D is 0.6 or more. It is an electron withdrawing group. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. Y is either —O— or —NR ¹ — or —CR ² R ³ —, R ¹ , R ² , R ³ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a substituent, and Z Represents a substituted or unsubstituted alkylene group, and x represents 1 or 2. ] 8. The information recording medium according to claim 1, wherein the methine dye is an oxonol dye represented by general formula (C-V) or general formula (C-VI).
General formula (C-V)

Formula (C-VI)

[Wherein, C and D represent an electron-withdrawing group, which may be linked to each other to form a ring, and when not linked to each other, the sum of the Hammett σp values of C and D is 0.6 or more. It is an electron withdrawing group. R represents a substituent on the methine carbon, m ⁷¹ represents an integer of 0 to 1, n ⁷¹ represents an integer of 0 to 2m ⁷¹ +1, and when n ⁷¹ is an integer of 2 or more, a plurality of R are They may be the same as or different from each other, and may be linked to each other to form a ring. Y ^{t +} represents a t-valent cation, and t represents an integer of 1 to 10. R ^{4 to} R ⁷ each independently represents a hydrogen atom or a substituent, and G represents an oxygen atom or a sulfur atom. ] The information recording medium according to claim 7, wherein the m ⁷¹ is 0.   An optical information recording medium having a recording layer capable of recording information by irradiating a laser beam of 440 nm or less on a substrate, and a transparent disk-shaped substrate on which a pregroove having a track pitch of 0.2 to 0.5 μm is formed The surface on the side where the pregroove is provided contains a methine dye and an organic oxidant having a reduction potential nobler than −0.4 volts, the oxidation potential b volts of the methine dye and the reduction potential of the organic oxidant. 11. The recording layer according to claim 1, wherein the recording layer is combined so that a difference from a bolt satisfies a relational expression of 1.0 ≦ b−a ≦ 1.3. Heat mode type information recording medium.