TWI342562B - Photo-information recording medium and novel oxonol compounds - Google Patents

Description

1342562 发明Invention Description: (I) Field of the Invention The present invention relates to a heating type information recording medium and an information recording method capable of inputting (recording) or reading (reproducing) information using laser light of high energy density. More particularly, the present invention relates to a heated information recording medium suitable for a write-type digital versatile disc (DVD-R) which uses visible ray to record information. (ii) Prior Art Information recording media (CDs), which can only record information once by laser light, have been known since ancient times. The information recording medium is also called a write-on CD (so-called CD-R), and has the advantage of making a small number of CDs available at a general price and being quickly available when compared with the production of a conventional CD. With the recent popularization of computers, the demand is increasing. Big. A typical structure of the C D - R type information recording medium is a layer in which a recording layer made of an organic dye, a reflective layer made of a metal such as gold, and a resin protective layer are sequentially laminated on a transparent disk-shaped substrate. Secondly, the information recorded on the optical disc is a laser beam that emits light in the near-infrared range (laser light of a wavelength generally around 700 nm), and the recording layer is locally thermally deformed. In addition, the reading (reproduction) of information generally irradiates laser light of the same wavelength as that of the recording laser light, and detects different reflections of the portion (recording portion) where the recording layer is thermally deformed and the portion where the deformation is not performed (unrecorded portion). The rate is carried out. In recent years, it has been seeking to record high-density information recording media. In order to increase the recording density, it is extremely effective to make the optical path of the irradiated laser light small and torsion, and since the wavelength is shortened and the laser light can be slightly twisted, the theoretically high-density 5 _ 1342562 degree is extremely profitable. know. Therefore, development of a disc for recording and reproduction using a short-range laser light of a wavelength of 780 nm is known as a write-once type data/video/disc (so-called DVD-R) disc. The optical disc is formed on a transparent disc-shaped substrate having a diameter of 120 mm or a diameter of 80 mm which is formed by a pre-groove having a narrower tracking distance of 0.5 μm than that of CD-R. The recording layer, which is generally provided with a reflective layer and a protective layer on the recording layer, is manufactured by a structure in which a disk-shaped protective substrate having the same size as the optical disk is bonded to the recording layer with an adhesive on the inside. Then, the DVD-R records and reproduces by irradiating visible laser light (usually laser light of a wavelength range of 6 00 nm to 7 〇 Onm #), and can record a higher density than a CD-R type optical disc. When the DVD-R type information recording medium is compared with the conventional CD-R type, since it can record several times the amount of information, of course, it has a high recording sensitivity, especially when it is necessary to quickly process a large amount of information, and an error is required for high-speed recording. The incidence is small. Further, the recording layer made of the pigment generally has a low stability with respect to heat or light, and it is desired to develop a recording layer which can maintain the stability performance after a long period of time for heat or light. A DVD-R type information recording medium in which a recording layer made of quinoline blue pigment is not provided on a substrate is disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. By using the pigment compound, an information recording medium which records high sensitivity and local reflectance can be obtained. Further, an information recording medium in which a recording layer made of a quinoline dye compound is provided on a substrate is disclosed in JP-A-2008-2008 It has excellent recording characteristics, and after a long time, α·ί maintains stability and is well-known. 丨-6 - 1342562. In addition, a CD-R type information recording medium in which a recording layer made of an oxonol dye is provided on a substrate is shown in Japanese Laid-Open Patent Publication No. SHO 63-209-99. By using the pigment compound, the recording and reproducing characteristics of stability can be maintained after a long period of time. Here, it is described that an ammonium oxygen* heterophthalocyanine dye compound is introduced into a molecule in a salt form. Further, an oxonol dye compound having an optical recording medium having high light resistance and durability and capable of providing good recording characteristics is described in JP-A-2000-B 2 6 5 8 [Patent Document 4]. [Patent Document 1] JP-A-2006-209995 Japanese Unexamined Patent Application Publication No. Publication No. JP-A No. 2000-526 No. PCT Publication No. 2000-526-58 Compounds are reviewed for their performance. As a result, the DVD-R type optical information recording medium containing the dye compound in the recording layer has extremely excellent recording characteristics in the low-speed recording of the equal-speed and the double-speed, and has a high-speed recording time of 4 times or more. Excellent recording characteristics, but the variable scheduling and reflectance φ are not clear and have practical and sufficient performance. In order to maintain a good recording characteristic at a low speed recording of 1 to 2 times speed, and at the same time, in a high speed recording of 4 times or more, a good information recording medium, particularly a sufficient reflectance and a variable scheduling optical information recording medium, In the optical characteristics, the real part η of the complex refractive index (n + ik) is larger than the low-speed recording dye, and the imaginary part k is the same as or smaller than the low-speed dye. Here, when the low-speed recording is performed, _-7 1342562 (3) is the optical information recording medium described in (1) or (2), and the oxygen: medium pigment is not structured by the following formula (丨).

Dye1 '-L^Dye^-L-^Dye12 Q (where Dye1 i, Dye12, Dye) each represent an independent bird with a chromophore pigment residue, and the L 1 1 and L2 k systems are not independent. The chromophores bonded to these chromophores do not form a π-common system valence bond group. The n-form is not 〇~1〇. The integer k represents all integers of 〇~η, and the Q system represents charge neutralization. (1) The optical information recording medium of (3), wherein the dye residue represented by D ye ||, Dye12, Dye" of the general formula (1) is formed. The chromophore is at least one of quinoline blue pigment, merocyanine pigment, and oxonol pigment. (5) The optical information recording medium according to (3) or (4), wherein all of the chromophores of the dye residue represented by DyeU'Dye^'Dyen of the formula (1) are formed as an oxonol dye. (6) The optical information recording medium according to any one of (1) to (5), wherein the dye having the structure represented by the following formula (<5) is contained in the formula (6).

1342562 can be an unsubstituted phenyl group. In the general formula (1), Dye11, Dye12, and Dye2k each represent an independent pigment residue having a chromophore. The chromophore forming the dye residue represented by Dye11, Dye12, and Dye2k may be formed by any substance such as quinoline blue pigment, styryl dye, merocyanine dye, oxonol dye, phthalocyanine dye, azo dye, Azomethine dye, squalene pigment, metal chelate complex dye. The chromophore forming the dye residue represented by DyeM, Dye12, and Dye2k is preferably a quinoline blue dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, or a metal chelate dye. More preferably, the chromophore which forms a dye residue represented by Dye11 or Dye12' Dye2k is a quinoline blue pigment, a phthalocyanine dye, an oxaphthalocyanine dye, and is preferably a quinoline dye or an oxonol dye. The chromophore forming the pigment residue represented by Dye11 and Dye12' DyeZk may be the same or different, and the same is preferred. When the chromophore which forms the dye residue represented by Dye11' Dye12 or Dye2k is quinoline blue pigment, quinolin blue pigment represented by the following formula (3) is preferred. General formula (3) [chemical 4]

a~Ma

Ra1—N^M wherein, each of Za1 and Za2 represents an atomic group of a 5-carbon or 6-carbon nitrogen-containing heterocyclic ring, and these may be a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an anthracene ring, A thiazole ring or the like is condensed. - 1 2 -

Ra丨 and Ra2佴—with γ (preferably $ ρ 〃 no hydrogen atom, substituted or unsubstituted alkyl 1 king 滕 Ί 芷 ' ' Ethyl 'n-propyl, isopropyl, yl + is its dipentyl 'benzyl, 3 - benzyl, 4 - butyl, 3 · methyl, substituted ^ & h sulfobenzene Methyl, residue methyl, 5-decylpentyl), allyl I-substituted alkenyl (preferably, carbon number 2 to 2, for example, ethylene 2, for example, = substituted or unsubstituted The aromatic fine is carbonium 6~Caiji); the base; 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, I-strong, or unsubstituted Heterocyclic group (preferably, the carbon U example paper has a sulfhydryl group, a morpholine group, a fluorenyl group, a group, a, ^ ', preferably a hydrogen atom, a _substituted or unsubstituted ruthenium. a substituted sulfoalkyl group, a substituted or unsubstituted sulfoalkyl group, more preferably a substituted or unsubstituted alkyl group or an 'alkyl group. Λ Ή $ $ unsubstituted sulfo group

Each of Ma1~MaM represents an independent methine group, which may be substituted with a substituent having a substituent such as a carbon number of 1 to 20 (for example, a methyl group, an ethyl group, an isohalogen atom (for example, chlorine). , bromine, iodine, fluorine) 'nitro, carbon - to ~ 2 0 " ^ 7 · ϊ ^ oxy (such as methoxy, ethoxy), carbon number 6 ~ 26 兀. A # square base (for example a phenyl group, a 2-nyl group, a heterocyclic group having a carbon number of 〇~2〇 (for example, 2pyridin-3-ylpyridyl group), an aryloxy group having a carbon number of 6 to 20 (for example, phenoxycainyl), and a carbon number of 1 ~20 with an amine group (such as acetaminophen, benzhydrylamine), amidoxime group of carbon 戮1~20 (such as hydrazine, hydrazine-dimethylaminocarbamyl), Alkylthio group (e.g., methylthio group) having a hydroxyl group, a carboxyl group or a carbon number of from 20 to 20 is preferred, and a ring is formed with other methine groups or a ring is formed with a dichroic group.

The Ma1~Ma7 series each represent an independent unsubstituted, ethyl-like, methyl-]3- 1342562 substituted methine group. Each of n a 1 and n a2 represents an independent 0 or 1, preferably 0. k a 1 is an integer representing 0 to 3~. Preferably, it is an integer of 0 to 2, and more preferably 1 or 2. When k a 1 is 2 or more, M a 1 and M a2 may be the same or different. The q system represents the ion that neutralizes the charge, and the y system represents the necessary number of charge neutralization. Further, the form in which any of the hydrogen atoms constituting Za1, Za2, Ra1, Ra2, and Ma1 to Ma7 in the general formula (3) is removed can be bonded to the bonding group L1 1 and L2k which are the pigment residues of the general formula (1). Knot. When the chromophore forming the dye residue represented by Dye11, Dye12 or Dye2k is a merocyanine, the merocyanine represented by the following formula (4) is preferred. General formula (4)

Q 2a4 naw ka"

Qy wherein, the Za3 group represents a group of a nitrogen-containing heterocyclic ring of 5 carbons or 6 carbons, and the like is a ring-condensation ring such as a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an anthracene ring or a thiazole ring. Za<* indicates an atomic group forming an acid ring. Ra3 represents a hydrogen atom, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted =, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero

Ral' Ra2 is the same as any ~. The methine groups (preferably and ~μ,) which are independent of each table. Na铩 is 〇 or 1. The β system represents an integer of 〇 〜 3, preferably an integer of 〇 -14 - 1342562 〜2. The Q system indicates that the ion ' y system that neutralizes the charge indicates the necessary number of charge neutralization. When ka2 is 2 or more, Ma1. MaU is the same or different. Further, in the general formula (4), any hydrogen atom constituting the form of Za3, Za4, R?, Ma8~Ma|i can be removed, and Dye11 can be formed with the bonding groups L11, L2k which are the pigment residues of the formula (o). When the chromophore of the dye residue represented by Dye12 or Dye2k is an oxonol dye, the oxonol dye represented by the following formula (5) is preferred. Formula (5) [Chem. 6]

Zas / 〆,

Qy, wherein each of the Za5 and Za6 groups represents an independent group of atoms forming an acid nucleus, and the groups of Ma~Ma14 each represent an independent substituted or unsubstituted methine group (the above preferred embodiment is the same as Mai~Ma7) 〇~3 The integer is preferably an integer of 〇~2, and more preferably an integer of 丨~2. ^^" When 2 or more, Ma·2, Ma, 3 may be the same or different. Q system represents neutralization charge Ion, y is the necessary number of neutralization charges, and is in the general formula (5), π 1 danchang human cα 'a, R a J ' M aβ ~ h 2% atom The form is removed, and the dye residue of the formula (1) can be used to pass through a thiol group L u ' l 2 k. 1342562

Za1, Za2, and Za3, for example, an oxyheterochrome core having a carbon number of 3 to 25 (for example, 2-2-3-oxazolyl, 2-3-ethyloxazolyl, 2-3,4-diethyloxazole) , 2 - 3 -methylbenzooxazolyl 2 - 3 -sulfoethylbenzoxazolyl, 2 - 3 - sulfopropylbenzoxazolyl, 2 - 3 -methylthio Ethyl benzoxazolyl, 2 - 3 -methoxyethyl benzoxazolyl, 2 - 3 - sulfobutylbenzoxazolyl, 2 - 3 -methyl-β-naphthyl Azyl, 2-methyl-α-naphthyloxazolyl, 2-2-3-sulfopropyl-β-naphthyloxazolyl, 2 - 3 -sulfopropyl-β-naphthyloxazole , 2 - 3 - ( 3 -naphthyloxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazole , 2 - 5 -bromo-3-methylbenzoxazolyl, 2 - 3 -ethyl-5-methoxyoxa oxazolyl, 2-5-phenyl-3-sulfopropylbenzo Oxazolyl, 2-5-(4-brominated phenyl)-3-sulfobutylbenzoxazolyl, 2 - 3 -dimethyl-5,6-dimethylsulfonylbenzoxazolyl a thiazole core having a carbon number of 3 to 2 5 (for example, 2 - 3 -methylthiazolyl, 2 - 3 -ethylthiazolyl, 2 - sulfopropylthiazolyl, 2-3 -sulfoyl) Thiazolyl, 2-2-3 sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-2-3-carboxyethylthiazolyl , 2-3-methylphenylthiothiazolyl, 2-2-3-benzothiazolyl, 2-2-3-butylthiazolyl, 2-2-3-sulfopropylbenzothiazolyl, 2-3 - sulfobutylbenzothiazolyl, 2-2-3-β-naphthylthiazole φ, 2-2-3-sulfopropyl-γ-naphthylthiazolyl, 2-2-3-naphthyloxy Benzyl)benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro-3-methylbenzothiazolyl, 2-6-iodo-3-ethylbenzene Thiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-2-3-ethyl-5-methoxybenzothiazolyl, 2-5-phenyl-3-sulfopropylbenzene And thiazolyl, 2-5-(4-bromophenyl)-3-sulfobutylbenzothiazolyl, 2,3-dimethyl-5,6-dimethylsulfonylbenzothiazolyl, etc. Imidazolyl nucleus having 3 to 2 carbon atoms (for example, 2 - 1 , 3 -diethylimidazolyl, 2 - 1 , 3 -dimethylimidazolyl, 2 - 1 -16- 1342562 methylbenzimidazolyl) '2-1,3,4-Triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-],3,5-trimethylbenzimidazole 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro-1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl -5 -diamino-6-chlorinated benzimidazolyl, etc.), carbon number: 〇~3 0 of pseudo-fluorene nucleus (for example, 3,3-dimethylhypothyroid)' carbon number 9~2 5 a quinoline nucleus (eg, 2-1-methylquinolinyl, 2-1-ethylquinolinyl, 2-1-ethylquinolinyl, 2-1-methyl-6-chloroquinolinyl) , 2-1,3-diethylquinolinyl, 2-methoxy-6-methylsulfuryl quinolyl, 4-1-methylquinolinyl, 4-]-sulfoethylquinoline Base, 4-1-methyl gg-7-chloroquinolinyl, 4-1,8-diethylquinolinyl, 4-1-methyl-6-methylsulfuryl quinolyl, 4-]- a sulfopropyl quinolyl group or the like, a selenium azole having a carbon number of 3 to 25 (for example, a 2-2-3 benzoselenazolyl group, etc.), a pyridyl group having a carbon number of 5 to 25 (for example, a 2-pyridyl group) And the like, and a thiazolinyl 'oxazolinyl group, a selazoline group, an oxazoline nucleus, a carbazole nucleus, a benzoxazole nucleus, a thiadiazole nucleus' carbazole nucleus, a pyrimidine nucleus. These may be substituted, and the substituents are, for example, an alkyl group (e.g., methyl 'ethyl, propyl), a halogen atom (e.g., chlorine, bromine, iodine, fluorine), a nitro'-oxyl group (e.g., methoxy, B). Oxy) 'aryl (e.g., phenyl), heterocyclic (e.g., 2-pyridyl, 3-pyridyl ' ]-pyrrolyl, 2 _thienyl), aryloxy (e.g., phenoxy), anthracene Amine (for example, acetaminophen, benzhydrylamine), amine methyl (for example, N,N-dimethylaminecarbamyl), sulfo, sulfonylamino (for example, sylvestre) Aminosulfonyl (e.g., methylamine sulfonyl), a hydroxyl group, a carboxyl group, a k-thio group (e.g., methylthio group), a cyano group, and the like are preferred, and an oxaphthalocyanine core or an imidazole nucleus is preferred. These heterocyclic rings may be additionally condensed. The condensed ring is, for example, a benzene ring, a benzofuran cyclopyrrole ring, an anthracene ring, a thiene ring or the like.

The Za4, Za5, and Za6 lines each represent the necessary atomic group for the formation of an acidic nucleus, by 1342562 by James, The Theory of the Phoyographic Process, 4th Edition, Mark Milan, 1977, page 198. Specifically, for example, pyrazol-5-one, pyridin-3,5-dione, imidazolin-5-one, hydantoin 2 ^ or 4-sulfanylhydantoin, 2-iminooxazolin-4-one '2-oxazolin-5-one '2-' · sulfurized oxazoline-2,4-dione, isotonine, tannin, thi-3-butanone, thiazol-3-one-1 1 -dioxide, indole-2-one, indol-3-one, 2-carbonylcarbazole, 5,7-dicarbonyl-6,7-dihydrothiazolyl [3,2-a]pyrimidine, 3,4-Dihydroisoquinolin-4-one,], 3-dioxane-4,6-one (for example, merutonic acid, etc.), barbituric acid, 2-sulfided bar Biortic acid, coumarin-2,4-dione, oxazol-2-one, pyridinium [1,2 - a ]pyrimidine-1,3 -dione 'pyrazole [1 , 5 - b ] quin Oxazolone 'pyrazolylpyridine, 3-dicyanomethylidene-3-phenylpropionitrile, 5 or 6 carbon carbon ring (eg hexane-1,3-dione, pentane-1, 3- The core of diketone, indan-1,3-dione, etc., preferably pyrazol-5-one, barbituric acid, 2-sulfided barbituric acid, I,3-dioxazole-4 , 6-diketone. Specific examples of quinine blue pigment, phthalocyanine pigment and xanthene pigment, for example, FM Harmer, Heterocyclic C ompound - C ya η ί D Dyes and Related Compound, John & Wiley & Sons, New York, London, 1964 Recorder. In the formula (1), each of L 1 1 and L 2 k represents an independent divalent bond group, and there is no particular limitation except that a π-conjugated system is not formed between the bonded chromophores. The preferred one is an alkyl group (carbon number 1 to 2 0, such as methyl group, ethyl ethene, propyl group, butyl group), and aryl group (carbon number 6 to 2 6, such as benzene) Base, naphthyl), alkenyl group (carbon number 2 to 2 0, for example, vinyl group, propylene group), alkyne (carbon number 2 to 2 0 'e. exemplified ethynyl group, propyl group), - C 0 - -18- 1342562 N(R丨.' -CO-O-, -so2-N(ri, — ' _s〇2 〇_, _n(r,03)_c〇· n(r10)-,- S02-, -SO-, -s....〇·, _c〇..._n(RI05)·, heteroalkenyl group (carbon number 1 to 26, for example, 6-chloro-1, 3,5_tridecyl·2, a carbon number of 4-~1 适合 which is suitable for the species of the 4-diyl or pyrimidine-2,4_yl group or above, preferably

R

R 0 4 R1 (M system each represents a hydrogen atom of a single jx 'substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. Moreover, the bond group represented by L1 1 , L2k may be in the bond One or more of the two chromophores are present, and a plurality of bonds (preferably two) may be formed to form a ring. L1 1. Each has two alkyl groups (preferably for stretching) Preferably, the ethyl group is bonded to form a ring, wherein a 5-carbon or 6-carbon ring (preferably a cyclohexyl group) is more preferred than the 11-form in the formula (1) represents an integer of 〇 10, preferably. It is an integer of 〇~5, more preferably an integer of 0 to 3, and most preferably an integer of 0 to 2. In the general formula (1), k represents all integers of 〇~η. For example, when η is 2 k represents three integers of 〇, 1, and 2, and Dye2k and L2k each represent an independent chromophore of Dye2°, Dye21 'Dye22, and a bonding group of l", l21, and L22. When η is an integer of 2 or more Several Dye2k may be the same or different. When n is an integer of 2 or more, several L2k may be the same or different. In the general formula (Q in the 表示 represents the ion neutralizing the charge, y represents the necessary number of the neutralizing charge) . Whether the compound is a cation, an anion, or a positive ion charge system is related to a substituent of the compound. The ion system represented by Q in the general formulae (1) and (3) to (5) determines the charge of the corresponding dye molecule. When the cation is not anionic with the surface or when the pigment molecule is uncharged, Q does not exist 134256. The ion represented by Q is not particularly limited, and may be an ion formed by an inorganic compound or an organic compound. In addition, the charge of the ion represented by Q may be -valence or multivalent. The cation represented by Q, such as sodium ion, potassium ion metal ion, 4th ammonium ion, oxygen ion, ion. Anthracene ions such as cerium ions, squamous ions, selenium cerium ions, iodonium ions, etc. In addition, anions such as chloride ions, bromide ions, fluoride ions of fluoride ions, sulfate ions, phosphate ions, hydrogen phosphate Heteropolyacid ion such as ion, succinic acid ion 'maleic acid ion, fumaric acid ion, organic polyvalent anion of aromatic dicarboxylic acid ion, tetrafluoride phosphate ion · hexafluoride acid The cation shown by Q is preferably iron ion, and more preferably it is a 4-stage ammonium ion. The fourth-order ammonium ion is in the general formula (I - 4 ) of the Japanese Patent Publication No. 2 0 0 0 - 5 2 6 5 8 The 4,4,-dipyridinium cation and the 4,4, _ bis cation cation disclosed in JP-A-2002-59652 are more preferable. The anion shown by Q is a boron tetrafluoride ion, a hexafluorophosphate ion and The organic polyvalent anion is more preferably a 2 or a trivalent organic anion such as a naphthalene dicarboxylic acid derivative. The naphthalene dicarboxylate anion disclosed in JP-A-10-226170 Φ is more preferably used in a 2 or 3 valent organic anion. In the dye represented by the formula (1), an optical information recording medium containing a dye having a structure represented by the following formula (6) is preferred. General formula (6) 1342562

'1 Q, wherein Za^' Za22, Za23, and Za24 each represent an atomic group forming an acid nucleus independently, and Za21, Za22, and Za23' za24 are, for example, an acid nucleus set by Za5 and Za6 of the above formula (5). Specific examples. Further, it is preferable that, for example, the above-mentioned Za5 'Z6 is the same as "Μ21, Μ22, Μ23' Μ24, Μ25, Μ26, Μ2, 丨2, and the substituted or unsubstituted methine groups, Μ21, Μ22, Μ23, Μ24' Μ25, Μ26, and Μ21 are the same as those described for Ma1 to Ma7 of the above formula (3). L 1 1 is a double bond and does not form a divalent bond group of the π-conjugated system, and Llk and L2k of the above formula (1) are described as specific examples. The preferred examples are the same. The cKa2l and K2M systems each represent an independent integer of 〇~3, preferably an integer of 〇~2, and more preferably an integer of 1 or 2. When K21 and K22 are 2 or 3, several existing Ma21, Ma22, Ma25, and Ma26 may be the same or different. The Q system represents a neutral cation valence cation. Or 2Q represents a divalent cation. Q is, for example, a case where the Q of the formula (?) is a cation, as a specific example. The preferred examples are also the same. Further, the optical information recording medium in which the dye represented by the formula (1) is a dye represented by the formula (1) is most preferable. R M, R 12 and R 13 ' R 14 of the formula (2) each represent an independent hydrogen atom

丄 J 斗z:) b: Z, substituted 1 ~ a non-lightly substituted alkyl 'substituted or unsubstituted aryl, and substituted unsubstituted heterocyclic. R|>, RI2, r, 3 'Rl4 is substituted or not substituted by BV7, Ί, '1^, such as carbon number] ~ 2 0 alkyl (such as methyl, "•, C Base, butyl, isobutyl, 3-butyl, isopentyl, cyclopropyl, cyclohexyl, ~_ 'benyl, phenethyl) and R1I, RI2, rI3, Rl4焼 . . 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此Cyclooctyl or the like, or a heterocyclic ring (e.g., piperidinyl, chromanyl, morpholinyl, etc.). r,,,Rl2, rI3,

The alkyl group represented by R1 is preferably a chain alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group, more preferably a chain (linear or branched) alkyl group having a carbon number of 1 to 5, R11 and Rl2 and Rl3 and RM each have no carbon number of the ring to form a ring]~8 cyclic alkyl group (preferably a cyclohexyl ring)' substituted alkyl group having a carbon number of 1 to 20 (e.g., benzyl, benzene) Ethyl). The substituted or unsubstituted aryl group represented by the formula (2), R12, RU ' Ri4 is, for example, an aryl group having 6 to 20 carbon atoms (e.g., phenyl, naphthyl). The aryl group represented by ru, R13 or R14 is preferably an aryl group having 6 to 10 carbon atoms. The substituted or unsubstituted heterocyclic group represented by R 1 1 ' R 12 and R 13 ' R 1 4 of the formula (2) has a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. a saturated or partially saturated heterocyclic group of the ring, such as a strong base, a π π group, a fluorenyl group, a piperidinyl group, a tridecyl 'pyrrolyl group, an imidazolyl group, a triazolyl group, a fluorenyl group, a thienyl group, a thiazolyl group. , oxazolyl, isothiazolyl, isoxazolyl and the like. Further, these are benzo condensed rings (e.g., quinolyl, benzopyrene D, benzothiazolyl'benzoxanthene, etc.). The substituted or unsubstituted heterocyclic group represented by W, R12, R 13 and R 14 is preferably a substituted or unsubstituted hetero-22-34242562 ring having a carbon number of 6 to 10. The substituent of the substituted or unsubstituted polyphenyl group, the substituted or unsubstituted aryl group, and the substituted or unsubstituted heterocyclic group represented by Ru, Rls, and R14 of the formula (2), for example, The substituent group S is described. The substituent represented by S includes an alkyl group having 1 to 2 carbon atoms (for example, a methyl group, an ethyl 'propyl group residue methyl group, an ethoxycarbonylmethyl group), and a carbon number 7 to a square alkyl group. (e.g., benzyl, phenethyl), alkoxy having a carbon number of 丨8 (e.g., methoxy, ethoxy), aryl having 6 to 2 carbon atoms (e.g., phenyl, naphthyl), carbon 6 to 20 aryloxy (e.g., phenoxy, naphthyloxy), heterocyclic (e.g., pyridinyl, pyrimidinyl, pyridyl, benzimidazolyl, benzothiazolyl, benzox Azolyl ' 2 -pyrrolidone-yl, 2 -piperidone-;!-based, 2,4-diisoimidazole -3-yl, 2,4-dioxazolyl-3-yl, horn shark Imine, ruthenium imidate, maleimide, halogen atom (for example, fluorine, chlorine, bromine, iodine), carboxyl group 2 to 10 alkoxycarbonyl group (for example, methoxycarbonyl, ethoxy) a carbonyl group, a cyano group, a fluorenyl group having 2 to 10 carbon atoms (e.g., an ethyl fluorenyl group, a pentyl group), an amine carbaryl group having a carbon number of 1 to 10 (e.g., an amine carbaryl group, a methylamine carbhydryl group) , morpholinylcarbamyl), amine group, substituted amino group having 1 to 20 carbon atoms (for example, two Methyl 0 amine, diethylamino, bis(methylsulfonylethyl)amine, N-ethyl-fluorene'-sulfoethylamino), sulfo, hydroxy 'nitro, carbon An alkylsulfonylamino group (for example, methylsulfonylamino) having 1 to 1 Å, and an aminomethylamino group having 1 to 1 carbon; for example, an aminomethylamino group, methylamine A a mercaptoamine group, a sulfonyl group having a carbon number of 1 to 1 (for example, a methanesulfonyl group, an ethanesulfonyl group), a carbon number of 1 to 〇, an aminesulfonyl group, and a methanesulfonyl group. When it is a carboxyl group or a sulfonium, these are in a salt state. -23 代咦未:(2) 'R2', R22, R3 each represent an independent hydrogen atom, a protected or a di-ortho group, a substituted or unsubstituted alkoxy group, a substituted group, a substituted Or unsubstituted aryloxy group, substituted thiol group, dentinogen h residue, substituted or unsubstituted 1 yl group, an aryl group, a substituted or unsubstituted aryl group, a furnace base, Substituted unsubstituted amine methyl, amino, substituted amine, disc, nitro, substituted or unsubstituted, deuterated amine-based furnaces substituted for Z-substituted amines Substituted or unsubstituted 'substituted substituted or unsubstituted arylsulfonyl, 'substituted or unsubstituted' sulfinyl and substituted or unsubstituted sulfonyl. R2, R22, U are substituted or unsubstituted with a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms. Alkoxy group having 1 to 2 carbon atoms, substituted or unsubstituted aryl group having 6 to W carbon atoms, preferably a halogen atom, more preferably an argon atom, substituted or unsubstituted carbon number 1 〜1 〇alkyl-substituted or unsubstituted carbon number i~(VIII) h-oxy-substituted or unsubstituted carbon number 2~丨〇 heterocyclic group, national atom, the best one is a hydrogen atom, a substituted or unsubstituted 1-5 of a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted carbon number of 2 to 6 Base 'and halogen atoms. R22 may further have a substituent, and as the substituent, for example, the above substituent group S. When m is 0, it is preferred that R21 'R22 is a hydrogen atom. Further, when ^ is 1, R21, R22 and R3 are preferably each a hydrogen atom. m of the formula (2) represents an integer of 0 or more, preferably an integer of 〇~5 (〇5 or more), more preferably an integer of 〇~3, and the most preferable one is 〇~: -24- 1342562 The integer. In the formula (2), when m is 2 or more, R3 may be the same or different and each represents an independent hydrogen atom or the above substituent. In the general formula (2), Zx + represents a cation, and X represents an integer of 1 or more. The cation represented by 'ZX + can be, for example, a cation represented by Q of the formula (1). The cation represented by zx + is preferably a quaternary ammonium ion, and more preferably a 4,4,-dipyridinium cation represented by the formula (1-4) in JP-A-2000-5265 No. 8 and a special 2 002-5 The 4,4'-dipyridinium cation disclosed in the publication No. 9652. In the formula U), X is preferably 1 or 2. The pigment represented by the formula (2) of the invention of the invention is a novel compound which has been synthesized by the present inventors. In the following, preferred examples of the compound represented by the formula (1) or the formulae (2) and (6) of the present invention are not limited thereto.

1342562 【化8】

-26 1342562 【化9】

(7)

-2 1342562

-28 1342562

Q 1342562 【化1 2】 (17) (18) (19)

-30- 1342562 【化1 3】 (20) Ο

(twenty one)

1342562

3 2 1342562 > 羼 【化1 5 (24)

Ή9 ¢4%

N-C4He I C<HS (25)

-33- 1342562 【化1 6】

(27)

-34 1342562

- 35- 1342562

1342562 【化】9】 (33)

3 7 1342562 【化20】 (3 4)

(3 5)

(3 6)

-3S 1342562 A general oxonol dye moiety can be synthesized by a condensation reaction of the active methine compound with a methine source (a compound used for introducing a methine group into a methine dye). For details of the compound, refer to Japanese Patent No. 3 9 - 2 2 0 6 9-, No. 43-3504, No. 54-38129, and No. 55-10059 'The same 58-* · 35544, Special Kai 49 -99620, the same as 52-92716, the same as 59-16834, the same as 63-316853, the same as the 64-40827, and the British Patent No. 1133986, the United States Patent No. 32472127, the same as No. 4042397 'the same 4181225 In the patent documents such as No. 5,213,956 and No. 5,260,179, the formulas of the general formulas (3) to (5) are used in the patent documents such as International Publication No. 02/08 1 61, Special Open 63-209995, and Special Kaiping 2-622M. Recorder. The synthesis of the dye compound represented by the formula (2) of the present invention can be carried out in the following scheme. [Chem. 2 1]

-39- 1342562

Further, when a pigment portion having more chromophores than the pigment portion 3-oxime is obtained, the reaction portion 2-1 is replaced with the bonding portion 2-1 of the above scheme (2) in the reaction of the compound 3-1 and the compound 1-1. Compound 1-1. 【化24】

The dye compound represented by the above formula (2) of the present invention may be used singly or in combination of two or more kinds. Further, the pigment compound of the present invention and the pigment compound other than -40-1342562 may be used. The information recording medium of the present invention may be any one having the above-mentioned dye compound as a recording layer, and the optical information recording medium having no particular limitation is used in c D · R to form a thickness i of a pre-groove of ~1.8 μm. The .2±0.2 mm transparent circle sequence preferably has a structure in which the dye layer and the protective layer of the dye compound represented by the above formula (2) are contained. Moreover, it is preferable to use two forms of DVD. (1) A recording layer and a light of the dye compound represented by the above formula (1) on the inside of the recording layer on a transparent disk-shaped substrate having a groove pitch of 0.6 to 0.9 μm The reflective layer body is formed into a light information recording medium (2) having a thickness of 1.2 ± 0.2 mm, and is formed on a transparent disk-shaped substrate of 0.6 ± 0.1 mm having a groove pitch of 6.6 to 〇·9 μηι. The laminated body of the recording layer and the light-reflecting layer of the compound and the transparent disk-shaped protective substrate having the same shape as the disk-shaped substrate are bonded to each other to form an optical information recording medium having a thickness of 1·2±〇2 mm. In the information recording medium, it can be constructed in the light protection layer. The information recording medium of the present invention can be arbitrarily selected from various materials which are conventionally used as information boards by, for example, the following panels (including a protective substrate). a substrate material such as glass; an acrylic resin such as polymethyl propyl methacrylate; a chlorinated vinyl resin such as a polycondensation ethane-based copolymer; and an epoxy resin according to the formula (2). The present invention has a groove pitch, a recording layer on the disk-shaped substrate, and a light-reverse R, and a thickness of the groove formed by the thickness of the two-layered groove containing the layer (1). Inside the recording layer!. Moreover, it is additionally fabricated on the f layer. The base of the recording medium; carbonate, chlorinated b: amorphous poly 1342562 olefin and polyester, etc., can be used as needed. A substrate which is film-like or rigid can be used. For the purpose of moisture resistance, dimensional stability and price, a material such as polymethyl methacrylate, which is provided on the surface of the substrate on which the polycarbon® is provided with the recording layer side, for the purpose of changing the force and preventing deterioration of the recording layer, Acrylate, styrene·maleic acid copolymer, polyvinyl alcohol amine, styrene·vinyl toluene copolymer, clopidogrel, polychlorinated vinyl, chlorinated polyolefin, polyvinyl acetate. Vinyl chloride The base copolymer 'ethylene vinegar $ such as ethylene, polypropylene, polycarbonate and other polymer materials such as surface modifiers. The undercoat layer is applied to the substrate after the preparation of the coating solution, and the coating liquid is applied to the substrate by a coating method such as extrusion coating of the stomach. A coating (pre-groove) that forms information such as a tracking mark is formed on the coating. When the pre-groove #material is injection-molded or extruded, the pre-concave layer can be used to pre-concave the material, and the monoester, diester, and monomer (or oligomer) of acrylic acid can be used. Opening with a photopolymerization initiator, for example, a pre-made master mold (a mixture of a mixture of a negative acid and a polymerization initiator), and after a cold plate, is borrowed through a substrate or a mother mold. The substrate and the coating layer are solidified by the curing of 'a. Then, among these materials, the above materials are preferred. The good flatness and the improved adhesion of the undercoat layer. Methacrylic acid copolymerization, N-methylol propylene oxime polyethylene, nitrocellulose ester 'polyimine, vinyl acetate copolymer, quality; and decane coupling dissolved or dispersed in solution spin coating 'dip coating 3 It is preferably formed by using a trench or a web site for the pitch of the resin traces such as polycarbonate. The formation of the groove. At least a mixture of the pre-groove triesters and the tetraester. The pre-groove I) is coated by the above-mentioned C. The coating liquid layer is sprayed with ultraviolet rays to cause coating by the substrate The mold 1342256 has a peeling effect. The pigment of the first aspect of the patent application is provided on the surface of the substrate (or the undercoat layer) on which the pre-groove is formed, and preferably the pigment compound of the above formula (I) of the present invention is contained. The recording layer. The recording layer may further contain various anti-fading agents for improving light resistance. A metal complex, a cerium salt, an ammonium salt or a tetracycline represented by the general formula (III), (IV) or (V) described in JP-A No. 3-2 2 4 7 9 3, for example, is known. The nitroso compound disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2-3, No. Hei. The recording layer is formed by dissolving the pigment of the present invention, depending on the required quenching agent, bonding agent, etc., in a solvent to prepare a coating liquid, and then applying the coating liquid onto the surface of the substrate to form a coating film. Drying is carried out. a solvent of a coating liquid for forming a dye recording layer, such as an ester of butyl acetate, ethyl lactate or a cellosolve acetate; a ketone of methyl ethyl ketone, cyclohexanone or methyl isobutyl ketone; a chlorinated hydrocarbon such as methane, 1,2-dichloroethane or chloroform; a guanamine such as dimethylamine; a hydrocarbon such as cyclohexanone; an ether such as tetrahydrofuran, diethyl ether or dioxane; , n-propanol, isopropanol, n-butanol, diacetone alcohol, etc.; 2,2,3,3-tetrafluoropropanol and other fluorine-based solvents; ethylene glycol monomethyl ether 'ethylene glycol monoethyl ether, propylene glycol Alkenyl ethers and the like. The solvent may be used singly or in combination of two or more kinds in view of the solubility of the compound to be used. Various additives such as an antioxidant, a U V absorbent, a plasticizer, a lubricant, and the like are added to the coating liquid depending on the purpose. a bonding agent such as gelatin, a cellulose derivative, a natural organic polymer substance such as dextran, rosin, rubber - 4 3 _ 1342562, and a hydrocarbon resin such as polyethylene, polypropylene, polystyrene or polyisobutylene. ; a vinyl resin such as a polychlorinated vinyl chloride, a polychlorinated vinylidene chloride, a polyvinyl chloride/polyvinyl acetate copolymer; an acrylic resin such as a polymethyl acrylate polymethyl methacrylate; a polyvinyl alcohol or a chlorine; A synthetic organic polymer such as an initial condensate of a thermosetting resin such as a polyethylene 'epoxy resin' butyraldehyde resin, a rubber derivative, a phenol or a formaldehyde resin. When the material of the recording layer and the bonding agent are used, the amount of the bonding agent is generally 1 to 50 times (mass ratio), preferably 1 to 5 times (mass ratio). ratio). The pigment concentration of the coating liquid thus prepared is generally from 0.01 to 10% by mass, preferably from 0.1 to 5% by mass. The coating method is, for example, a spray method, a spin coating method, a dipping method, a roll coating method, a blade coating method, a knife coating method, a screen printing method, or the like. The recording layer can be a single layer or a plurality of layers. The layer thickness of the recording layer is generally 20 to 500 nm, preferably 50 to 300 nm. A reflective layer is provided for the purpose of improving the reflectance at the time of information reproduction on the above recording layer. The light-reflecting substance of the reflective layer material is a substance having high reflectance for laser light, such as Mg, Se, Y'Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Μη, Re, Fe. Metals such as Co, Ni, Ru, Rh, Pd, Ir 'Pt, C u 'Ag, Au, Zn, Cd, A1, Ga, In, S i ' Ge, Te, Pb, P〇, Sn ' Semi-metallic or stainless steel. Preferred among these are (: 1', >^, ?1' (: 11, six §, six 11, six, and stainless steel), and more preferably A g. These materials can be used alone. Or a combination of two or more, or used as an alloy. The reflective layer can be formed, for example, by subjecting the above-mentioned reflective material to vapor deposition, sputtering or ion coating on the recording layer. The thickness of the reflective layer is - 44-1342562. It is 〇~300 nm, preferably 50 to 200 nm. A protective layer may be provided for the purpose of physically and chemically protecting the recording layer on the reflective layer. The protective layer is intended to improve scratch resistance and moisture resistance. The material used for the recording layer may be, for example, an inorganic substance such as SiO, SiO 2 , MgF 2 , SnO 2 or Sis N 4 , or an organic substance such as a thermoplastic resin, a thermosetting resin or a UV curable resin. The protective layer can be formed, for example, by laminating a film obtained by plastic extrusion on the reflective layer and/or on the substrate, or can be provided by vacuum evaporation, sputtering, coating, etc. Moreover, it is thermoplastic. When resin or thermosetting resin is dissolved in After preparing the coating liquid in a suitable solvent, the coating liquid is formed by coating and drying. When the UV curable resin is used, the coating liquid is prepared by directly or after dissolving in a suitable solvent to prepare the coating liquid. The liquid is cured by irradiation with UV light. In the coating liquid, various additives such as an antistatic agent, an antioxidant, a UV absorber, etc. may be added depending on the purpose. The thickness of the protective layer is generally 0.1 to ΙΟΟμηι. In the above-mentioned process, a laminate in which a recording layer, a reflective layer, and a protective layer as required are provided on a substrate can be produced. Two laminated bodies are produced as described above, and these adhesives are attached to each record by bonding them. On the inner side of the layer, a DVD-R type information recording medium having a two-layer recording layer can be manufactured. Further, the obtained laminated body and a disk-shaped protective substrate having the same size as the substrate of the laminated body are bonded to the recording layer with an adhesive. On the inner side, a DVD-R type information recording medium having a recording layer on only one side can be produced. The information recording method of the present invention is performed using the above information recording medium, for example, as follows. First, the information recording medium is aligned. The scanning or the angular velocity is twirled, and the substrate laser side is irradiated with laser light such as semiconductor laser light, etc. -45- 1342562. This is formed by the light to form a cavity at the interface between the recording layer and the reflective layer (the cavity is formed with a substrate) The thickness is deformed, or the recording layer is discolored, and the rendezvous state is formed, or the refractive index changes due to the deformation of the substrate thickness, the discoloration of the recording layer, the change of the state of the recording, etc., to record information. The recording light system CD-R can be used. ~790nm, DVD-R type uses a semiconductor laser beam of 600~700nm (preferably 62〇~6 80nm', preferably 63〇~660nm). The information reproduction can be borrowed as described above. The detection of the reflected light is performed by causing the information recording medium to rotate at the same alignment speed as described above and to irradiate the semiconductor laser light having the same wavelength as that at the time of recording from the substrate side. [Examples] [Example 1] Synthesis of Compound (3) The synthesis of the compound of the present invention was carried out in the above scheme. [bonding portion (synthesis of compound (1-1)) 1,4 cyclohexanedione (22.43 g, 〇. 2 mol) and malonic acid (41.62 g, 0 · 4 m ο 1) were dissolved in acetic acid Anhydride (85 m 1 ) was added with concentrated sulfuric acid (7 · 0 m 1, 0 · 1 2 m ο 1) and stirred in an ice bath. Since the reaction was carried out with the reaction of light brown crystals, the material was filtered, washed with ice-cold distilled water, and dried to obtain 8.8 g of the compound 1-1 of pale brown crystals (yield 15.5 %). [Synthesis of the dyed part (Compound (3-11))] Malonic acid (10 ml) was added with malonic acid (5.2 g, 〇.〇5 ml) and concentrated sulfuric acid '(°·5ηι1), and stirred at room temperature. After the starting compound was completely dissolved, it was cooled in an ice bath and 4 - ethylcyclohexanone (6.3 1 g, 0.05 m ο 1) was slowly added dropwise. When stirring was continued in an ice bath, when the colorless crystal was precipitated with the reaction, the material was filtered, washed with distilled water, and dried to obtain 9.0 g (yield: 85.1%) of meruton. Colorless crystals of derivatives. The obtained merutonic acid derivative (4.25 g, 0.02 m〇l) and N,N'-1,3-pentadiene-buki-5-nonanediphenylamine hydrochloride (5.7 〇g, 〇 · 〇2 m ο 1) Dissolved in methanol (5 〇m丨), added with triethylamine (3.04 g, 0.03 mol), and after stirring at room temperature, purple crystals were precipitated, and the material was filtered and washed with methanol. A purple crystal of 5 · 6 ig compound (3 -1) was obtained (yield 7 6 · 3 %). The purple crystal (4.4 〇g ' 1 2.0 mm ο 1) and the compound (1-I) (1.71 g, 6.0 mmol) shown in the above synthesis example were dissolved in dimethylformamide (20 ml), and the mixture was added dropwise to triethylamine. After the amine (1.82 g, 8 mmol) was stirred at 50 ° C for 4 hours, distilled water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extracted organic layer was purified by silica gel chromatography (dichloromethane/methanol = 6 / 1) to yield 2.0 g (yield 39. [Synthesis of Pigment Compound] The purple powder (1.24 g, 1.48 mmol) synthesized above was dissolved in dimethylformamide having a minimum dissolved amount, and Compound C used for the cation was added thereto, followed by stirring at room temperature. When the stirring was continued, the material was filtered to precipitate a gold powder, and 0.95 g of the golden powder of the compound (3) was obtained (yield 48.3 %) ° 1342562

The obtained gold powder was confirmed to have a structure by 1 Η N M R . 1 H NMR (DMSO - d6) : 0.84 (t, 6 Η), 1.20 (m, 10H), 1.62 (m.8H), 1.96 to 2.14 (m.) 2H), 7.24 (d, 2H), 7.34 ~7.77 (m, 18H), 7.90 (d, 2H), 9.00 (d, 2H), 9.65 (d, 4H), 1 0.7 1 (s, 2H) [Example 2] Compounds (1), (3) And (14) in the synthesis of the compound (3) shown in Example 1, using cyclohexanone in place of 4-ethylcyclohexanone for synthesis, by using the sand column chromatography of the scheme (3) In the purification of the method, the compound of the pigment anion of the compound (I) is separated from the compound of the compound (13) or the pigment anion of the compound (14). The obtained compound of the -48-1342562 pigment anion is chlorinated by the scheme (4) to synthesize the compound (1), the compound (13) and the compound (14). Compound (1) HNMR (DMS0-d6): 1.4 〇 (s'4H), 1.54 (s, 8H)' 1. 83 (s, 8H), 1.98 (s, 8H), 7.09 to 7.79 (m, 24H), 7.92 (s, 2H), 9.00 (s, 4H), 9.69 (s, 4H) 1H NMR (DMSO - d6) of compound (13): 1.4 l (s, 4H), 1.53 (s, 8H) , 1.98 (s, 24H), 7.13 (t, 8H), 7.38 ~ 7.79 (m, 40H)' 7.91 (s, 4H), 9.0 1 (d, 8H), 9.67 (d, 8H), 1 0.74 (s , 4H)

[Example 3] Synthesis of Compound (2) In the synthesis method of Compound (3) shown in Example 1, except that 4-methylcyclohexanone was used instead of 4-ethylcyclohexanone, the same as Example 1. Compound (2) is synthesized. 1H NMR (DMSO - d6): 0.91 (d, 6H), 1.20 (q, 4H), 1.47 (s, 2H), 1.65 (m, 8H), 2.01 (m, 12H), 7.28 (d, 2H), 7.39~7.86(m,

1 8H) ' 7.89 (s, 2H), 9.01 (d, 4H) ' 9.67 (d, 4H), 1 0.7 1 (s, 2H) [Example 4] Synthesis of Compound (4) is shown in Example 1. In the synthesis method of the compound (3), the compound (4) was synthesized in the same manner as in the Example except that menthone was used instead of 4-ethylcyclohexanone. 1H NMR (DMSO - d6): 0.81 (t, 12H), 0-90 (d, 8H), 1.21 (t, 2H), 1.41 (s, 4H), 1.61 (t, 4H), 1.72 (d, 2H), 1.97(s,8H), 2.18(d,4H), 7.12(q,4H), 7.24(d,2H), 7.38~7.78(m,18H), 7.90(s, 2H), 9.01(d,4H) 9.6 8(d, 4H), 〇.71(s, 2H) -4 9 -1342562 [Example 5] The synthesis of the compound (5) is carried out in the synthesis method of the compound (3) shown in Example 1, except The compound (5) was synthesized in the same manner as in Example except that 3,3,5-indole-trimethylcyclohexanone was used instead of 4-ethylcyclohexanone. 1H NMR (DMS 〇-d6): 0.89 (1,12H), 〇.97 (s, 6H), 1.40 (m, 4H), 1.89 to 1.98 (m, 16H), 7.11 (m, 4H)' 7. 26(d, 2H), 7.40 (d, 2H), 7.49 (m, 6H), 7.60 (t, 4H), 7.70 (m, 6H), 7.90 (s, 2H), 9.00 (s, 4H), 9.67 (s, 4H), 1〇.72(s, 2H) φ The synthesis of the compound (6) is carried out in the synthesis of the compound (3) shown in Example 1, except that methyl ethyl ketone is used instead of 4-ethylcyclohexane. Compound (6) was synthesized in the same manner as in Example 1 〇lHNMR (DMS0-d6): 〇.95 (t, 6H)' 1.53 (s, 6H), 1.81 (t, 4H), 1.99 (s, 8H) ) 7.11(q,4H), 7.26(d,2H)' 7.39 ~7.77(m, 18H), 7.89(s,2H), 9.00(d,4H), 9.67(d,4H)' I0.69( s, 2H) [Example 7] ® In the synthesis method of the compound (3) shown in Example 1, except that 3,3 '-dimethyl-2-butanone was used in place of 4-ethylcyclohexanone, Compound (7) was synthesized in the same manner as in Example 1. 1H NMR (DMSO - d6): ll 〇 (s, 18H), 1.51 (s, 6H), .98 (s, 8H), 7.14 (q, 4H) '7.28 (d, 2H), 7.38~7.78 ( m, 18H), 7.90 (s, 2H), 9.01 (d, 4H), 9.79 (d, 4H), 1 0.7 1 (s, 2H) [Example 8] -5 0 - 1342562 Synthesis of Compound (8) In the synthesis method of the compound (3) shown in Example 1, the compound (8) was synthesized in the same manner as in Example 1 except that 2-ethylcyclopentanone was used instead of 4-ethylcyclohexanone. 1Η NMR (DMS〇-d6): 0.90 (m, 18 Η), 1.83 (q, 4H), 2.00 (s, 8H), 2.15 (m, 2H), 7.1] (q, 4H), 7.26 (d, 2H) ), 7.38~7.75 (m, 1 8H), 7.90 (s, 2H), 9.01 (d' 4H), 9.68 (d, 4H), 1 〇.7 〇 (s, 2H) [Example 9] Compound ( 9) Synthesis of Compound (9) was carried out in the same manner as in Example 1 except that diethyl ether was used instead of 4-ethylcyclohexanone in the synthesis of the compound (3) shown in Example 1. 1H NMR (DMSO - d6): 0.85 (t, 12H)' 1.84 (q, 8H)' 2.00 (s, 8H), 7.11 (q, 4H), 7.26 (d, 2H), 7.32 to 7.78 (m, 18H) ), 7.89 (s, 2H), 9.00 (d, 2H)' 9.66 (d, 2H), 1 0.70 (s, 2H) [Example 1 0] Compound (10) was synthesized in the compound shown in Example 1. In the synthesis method of (3), the compound (10) was synthesized in the same manner as in Example 1 except that 2-pentanone was used instead of 4-ethylcyclohexanone. 〇1H NMR (DMSO - d6): 0.90 (t, 6H) , 1.45 (s, 6H), 1.77 (m, 4H), 1.98 (s, 8H), 7.10 (q, 4H), 7.27 (d, 2H), 7.40 to 7.80 (m, 18H), 7.91 (s, 2H) ), 9.05 (d, 4H), 9.65 (d, 4H)'] 0.72 (s, 2H) [Examples] 1] Synthesis of Compound (1 1 ;) -51' 1342562 Compound (3) In the synthesis method, the compound (1 1 ) was synthesized in the same manner as in Example 1 except that 3-ethylcyclohexanone was used instead of 4-ethylcyclohexanone. 1H NMR (DMSO - d6) _· 〇 '98 (m, 8H), l'28 (t, 2H), 1.50 · · ~^ "(m,]0H), 1.96 ~ 2.08 (m, 12H), 7.11 (m, 4H), 7.38 to 773 (m, 18H), 7.90 (s, 2H), 9. 〇〇 (s, 4H), 9.66 (s, 4H), 1 〇 · 70 (δ) 2H) Example 1 2] Synthesis of Compound (1 2 ) Φ In the synthesis method of the compound (3) shown in Example 1, except that cyclohexanone was used instead of 4-ethylcyclohexanone, 3-methyl 4 was used, and ? '-1,5-Heptadien-1-yl-7-guanosine diphenylamine hydrochloride substituted N,N'-1,3-pentadien-1-yl-7-xanthene diphenylamine hydrochloride The compound (1 2) was synthesized in the same manner as in Example 1. lHNMR (DMSO-d6): 1.41 (s, 4H), 1.58 (s, 8H), 1.82 (s, 8H), 1.99 (s, 8H), 2.17(s,6H), 7.24~7.48(m, 12H), 7.69~7.99(s,]2H), 9.00(s, 4H), 9.68(s, 4H), l〇.71(s, 2H) Example I 3] Φ optical property evaluation of the optical properties of the pigment compound of the present invention (the real part n and the imaginary part k of the complex refractive index), which is evaluated by a reflection-type spectroscopic ellipsometry method. The optical property evaluation sample is used to form a film on a glass substrate. 'Rotating coating film. The spin coating film dissolves the compound having a solution concentration of 25 mM in 2,2,3,3-tetrafluoropropanol, and casts the solution on a rotating glass substrate. -52 1342562 [Preparation of spin coating film containing comparative compound (1)] A spin coating film was prepared as a comparative example using a comparative compound (1) having the following structure having good recording characteristics in one-color recording. Further, a comparative compound (10 is 1-94 in JP-A-2002-24967, No. 4). Comparative Compound (1) [Chem. 2 6]

The optical properties of the spin coating films of the compounds (1) and (3) to (14) exemplified in the present invention were evaluated, and the results of η at 660 nm and k were as shown in Table 1 below.

-53 1342562 [Table 1] Compound N k Compound (1) 2.24 0.055 Compound (3) 2.23 0.054 Compound (4) 2.20 0.040 Compound (5) 2.20 0.038 Compound (6) 2.27 0.040 Compound (7) 2.22 0.041 Compound (8) 2.24 0.040 Compound (9) 2.25 0.047 Compound (10) 2.26 0.051 Compound (1 1) 2.2] 0.035 Compound (12) 2.21 0.051 Compound (13) 2.40 0.056 Compound (14) 2.30 0.050 Comparative compound (1) 2.08 0.051 An embodiment of an optical information recording medium. [Examples] 4] [Production of Optical Recording Medium] Polycarbonate resin was molded by injection molding to have a thickness of 螺旋6 mm, diameter 1 having a spiral groove (depth 1 30 nm, width 3 1 Onm 'tracking pitch 〇7_m) On a 20 mm substrate. 1.25 g of the color hydrazine compound (6) of the present invention was dissolved in 1 〇 1 m 1 2,2,3,3 -tetrafluoropropanol to prepare a coating liquid. Imitation 5 4 - The coating liquid was applied to the groove surface on which the above-mentioned substrate was formed by spin coating 1342562 to form a pigment layer. Then, silver was sputtered on each of the dye-coated surfaces to form a reflective layer having a film thickness of about 150 nm, and then an ultraviolet curable resin (manufactured by Lai Yakovia SD-640 Dainippon Ink Chemical Industry Co., Ltd.) was used as the adhesive. The agent is formed into a compact disc with a laminate substrate having a thickness of 6 mm. (Comparative Example 1) An optical disk was produced in the same manner as in Example 14 except that the above-mentioned comparative compound (1) was used instead of the dye compound (6). (Comparative Example 2) An optical disk was produced in the same manner as in Example 14 except that the above-mentioned comparative compound (1) and the following comparative compound (2) were mixed with the substituted dye compound (6) in a ratio of 6:4. Further, the comparative compound (2) is I-96 in JP-A-2002-249674. [Evaluation of Optical Recording Media] Using DDU1000 and complex signal generator (made by Parus Stichco. Laser wavelength = 660nm, aperture ratio = 0.60), transfer speed 1x speed (11.08Mbps), 8x speed ( 88.64M), double speed (ii〇.8Mbps) records 8-16 tone signal. The recording strategy plan used is shown in Table 2. 1 time speed recording, 1 〇 double speed recording is one type, and 8 times speed recording is recorded in two types with different pulsation widths. Record energy to set the minimum recording energy of the jet in various media. Then, the laser is regenerated using a laser having the same wavelength as the laser wavelength, and the air jet is measured. The results are shown in Table 3. -55- 1342562 In the case of the 1x speed, 8x speed, and 10x speed, the air jet was low and the reflectance was high as compared with the comparative example. Moreover, when the 8 X recording characteristic is recorded with a large pulsation width, the embodiment can obtain a good jet situation. In addition, when a single cycle signal of 3 Τ and 14 记录 is recorded at 12 times speed and 16 times speed, a C/N ratio equal to the multiple speed of 1 〇 、, a variable schedule, and a jet can be obtained. This is a good characteristic with a recording speed of at least 10 to 16 times or more. Recording speed IX 8X 8X ]〇X Snow? Recording Strategy Project ABCD 3Ttop 1.55 2.55 1.85 2.75 4Ttop 1.50 2,92 2.12 3.20 nT too 1.55 1.70 1.30 1.90 Tm η 0.65 _ - -1. ---- nT wt 0.50 -0.30 0.55 ηΤΙπ 1.40 0.60 1.40 " 1 VII - ----- 1-nTld -0.03 -0.05 -0.03 3T dtop -0.15 -0.05 -0.15 4Tdi〇P 0.20 0.35 0.20 nTdtop 0.00 0.00 0.00 5Tt〇D2 -0.15 -0.05 -0.20 STln? -0.10 -0.15 -0.20 J 1 ------*--1 5Tdl〇2 0.00 0.00 0.00 pn/Pm - 】.48 1.58 1.36 (Table 2) Recording strategy plan [Table 2]__ 1342562 Record data

3T > nTtop βτ nTt〇t> ····*^·ι 一\3-r])Tid :i . 7-----/ ~·j Ρο ¢:~ -H ζ- -Τιλο Recording Strategy Project AS writes 16 rushed nTtep <- multi-hTup order ηΤΙρ Ρ〇

Recording Strategy Plan B, C, D (Table 3) Recording Characteristics Evaluation Results [Table 3] Implementation 1 Column 14 Comparison Example 1 Comparison Example 2 Recording Speed IX 8X 8X 10X IX 8X 8X 10X IX 8X 8X 10X Recording Strategy Project ABCDABCDABCD The most recorded energy (mW) 11 28.5 36.3 33.5 12 28.0 39.0 34.0 7.9 25.5 29.5 29.2 Reflectance (%) 53.2 51.8 52.0 50.9 50 49.1 49.0 48.6 44.5 46.5 44.8 44.4 , > V eve (%) 6.1 6.2 6.0 7.2 9.0 13.2 12.0 15.0 8 13.9 6.8 9.0 14T variable scheduling 0.54 0.71 0.77 0.78 0.50 0.72 0.76 0.77 0.50 0.73 0.78 0.77 PI error 80 18 11 15 94 40 Measurement is not measurable Not determined 94 Measured 90 120 AR(%) 60 32 28 25 48 30 32 25 48 28 28 26 Comparative Compound (2) -57- 1342562 [Chem. 2 7]

[Example 1 5] The pigmentation % 'urn, described in Table 4 below, was used. ", 19, 21, 22, a mixture of Comparative Compounds 1 and 2 was substituted for the dye compound (6), and the same procedure as in Example 作 was used to prepare a disc sample 2〇2 to 2, which was evaluated in the same manner as in Example 14. The results of the regeneration were recorded. The results are shown in Table 4. When the dye of the present invention was compared with the comparative compound, it was found that the reflectance was high, the jet was low, and sufficient shift scheduling was obtained.

5 8' 1342562 蝎 [Table 4] Sample number Pigment number reflectance (%) Jet MT variable scheduling Remarks 201 Compound 6 50.9 7.2 0.76 The present invention (Example μ) 202 Compound 7 52.0 8.2 0.78 203 of the present invention 8 51.2 8.1 0 77. The present invention 204 Compound 9 52.2 7.9 0.77 The present invention 205 Compound 10 52.4 8.1 0.78 The present invention 206 Compound 5 53.1 7.8 0.77 The present invention 207 Compound 16 52.1 7.9 0,76 The present invention 208 Compound Π 53.9 8.4 0.75 The present invention 209 Compound 19 52.8 7.6 0,76 210 of the invention Compound 21 52.1 6.8 0.78 211 of the invention 22 221.6 8.1 0.78 212 of the invention Comparative compound 1 48.6 15.0 0,77 Comparative Example 213 Comparative compound], 2 44.4 9.0 0.77 Comparative example

Claims (1)

1342562 _. Amendment, 丨Wir Day Correction Replacement Buy j No. 092 133493 "Light Information Recording Media and Novel Oxygen Phthalocyanine Compounds" Patent Case (Revised on November 15, 2010) X. Application Patent Range: 1. A An optical information recording medium characterized by containing a dye represented by the following formula (2), and the formula (2) (wherein R11, R12, R13, and R14 each represent an independent hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic ring; One, R21, R22, R3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted one. An aryloxy group, a substituted or unsubstituted heterocyclic group, a halogen atom, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a cyano group, a substituted or unsubstituted fluorenyl group, substituted or unsubstituted Substituted amine formamidine, amine group, substituted amine group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonyl group Amine, substituted or unsubstituted aminemethantyl, substituted or unsubstituted sulfonyl 'substituted or unsubstituted aryl magnetic II, substituted or unsubstituted Alkylsulfinyl, substituted or unsubstituted arylsulfinyl and substituted or unsubstituted amine Acyl any -1--1342562 In the correction, m is an integer of 0 or more, and when m is 2 or more, R3 may be the same or different, Zx+ is a cation, and x is an integer of 1 or more. 2. The optical information recording medium of claim 1, which is of a heating type, and which is formed in a groove having a groove pitch of 0.6 to 0.9 μm, a diameter of 120 ± 3 mm or a diameter of 80 ± 3 mm, and a thickness. 6.6±0.1mm transparent disc-shaped substrate is provided with two laminated bodies formed on the surface of the pre-groove side and provided with a recording layer containing the pigment shown in the first item of the patent application, so that each recording layer becomes the inner side The bonding method is such that the thickness becomes 1.2 ± 0.2 mm. 3. The optical information recording medium of claim 1, which is of a heating type, wherein a pre-groove having a groove pitch of 0.6 to 0.9 μπ! has a diameter of 12 〇 ± 3 mm or a diameter of 80 ± 3 mm and a thickness of 0.6. A ±0.1 mm transparent disc-shaped substrate is provided with a laminate formed on the surface of the pre-groove side and provided with a recording layer containing the pigment shown in the first item of the patent application, and the disc-shaped protective sheet is placed inside the recording layer. The joint thickness is 1.2 ± 0.2 mm. 4. A oxindole compound characterized by the following general formula (2): general formula (2) 13 14 ((m+2)/x)Zx+ (wherein R each independently represents a hydrogen atom, R12, R'3, R-2 - 1342562 A modified, substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic ring, wherein R22, y represents a hydrogen atom, substituted or not Substituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic, halogen Atom, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, cyano group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted amide group, amine group, substituted amine group, sulfo group a hydroxy, nitro, substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted amine formamide, Substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted aryl Any of a sulfonyl group and a substituted or unsubstituted sulfonyl group, the m system represents an integer above 〇, m is 2 or more, a plurality of R3 may be identical or different, Zx + represents a cation based, χ represents an integer of 1 or more).