JP4431344B2 - Optical information recording method and optical information recording medium - Google Patents

Description

  The present invention relates to an optical information recording medium capable of writing information by laser light and a recording method thereof. In particular, the present invention relates to an optical information recording method for recording information using non-resonant two-photon or multi-photon absorption, and an optical information recording medium for recording information using the method.

  Conventionally, optical disks such as CD-R / RW and DVD-R / RW are known as recording media for recording information using laser light. In these optical discs, a laser having a wavelength of about 780 nm is used for the former and a wavelength of about 660 nm is used for the latter. In recent years, with the rapid development of information technology, there is an increasing demand for higher capacity and higher density recording media. In order to realize a high capacity and recording density, it is effective to reduce the radius of the laser beam for information recording as small as possible, but it is not possible to narrow it beyond the diffraction limit. It is theoretically known that the diffraction limit depends on the wavelength of light used, and is shorter as the wavelength is shorter. Therefore, development of an optical disc capable of recording / reproducing using a conventionally used laser having a wavelength shorter than 780 nm or 660 nm has been promoted. For example, an optical disc called a Blue-Ray Disk has been proposed. . The Blue-Ray Disk uses a laser having a wavelength of about 400 nm, and enables recording with a higher capacity and higher density than CD-R / RW and DVD-R / RW. However, the shortening of the laser wavelength has finally reached the 400 nm level, and it is difficult to further spread the short wavelength laser and develop the recording medium necessary for it, and even higher density can be achieved using existing lasers. Possible technology is needed.

  Therefore, it has been proposed to use a two-photon or multi-photon absorption process, which is one of nonlinear optical effects, as a means for obtaining a high-capacity and high-density information recording medium without using a short wavelength laser. Yes.

  Two-photon absorption is a phenomenon in which a molecule is excited by simultaneously absorbing two photons, and the molecule absorbs twice as much energy as a photon corresponding to the wavelength of the irradiated laser beam, so there is no linear absorption. It is possible to excite molecules even using light in a long wavelength region. Further, since the probability of occurrence of two-photon absorption is proportional to the square of the intensity of irradiated light, the intensity distribution of the laser light that induces two-photon absorption becomes a sharper shape with a narrowed half-value width. This corresponds to narrowing down the radius of the laser beam two-dimensionally, and information recording can be performed in a radius region smaller than the radius of the irradiated laser beam. Also, three-dimensionally, two-photon absorption is induced only in a very small region where the laser beam intensity of the laser beam is focused by a lens and is slightly off the focal position. Two-photon absorption can be selectively induced in an arbitrary minute space in a three-dimensional space. That is, recording / reproduction in the depth direction in the three-dimensional space becomes possible. Due to these properties, if two-photon absorption is used, in principle, higher-density information recording is possible without using a short-wavelength laser.

  As an optical information recording medium using two-photon absorption, for example, S.I. Kawata et al. Chem. Rev. As shown in 2002, 100, 1777 [Non-Patent Document 1], photochromic material is caused to absorb two-photons and two-photon photochromism of the compound is induced to detect an absorption change or a refractive index change. A system and a system in which the refractive index is changed by two-photon photopolymerization using a photopolymer have been proposed. In addition, WO 97/09043 [Patent Document 1] discloses an example of an optical recording medium that uses a change in absorption caused by two-photon absorption dye itself fading due to two-photon absorption. However, since these optical recording media use so-called photoreactions for information recording, for example, when light strikes after information recording, the recording reaction proceeds in an unrecorded part or reverse photochromism occurs. There is an essential problem that the recorded information is changed, for example, the recorded signal is lost due to the recording.

On the other hand, according to Hiroaki Misawa, O plus E, 1998, 20, No. 9, p. 1028 [Non-patent Document 2], when intense laser light is irradiated inside quartz glass, a chemical reaction due to two-photon absorption occurs. There has been proposed an optical memory that records information by occurring and changing the refractive index. In the recording medium, the chemical species generated by the photoreaction derived from the two-photon absorption is stable to both heat and light, but since the two-photon absorption efficiency of the glass material is extremely low, a high-power laser beam must be used. In addition to this, material design for improving the two-photon absorption efficiency and so-called molecular design for imparting various physical properties necessary for practical use are not easy.
International Publication No. 97/09043 Pamphlet S. Kawata et al. Chem. Rev. 2002, 100, 1777 Hiroaki Misawa, O plus E, 1998, 20 (9), 1028

  An object of the present invention is to provide a novel information recording method for providing a high-capacity, high-density, and light-stable information recording medium without using a short wavelength laser, and an information recording medium for realizing the information recording medium. It is to be.

  In the present invention, by using a non-resonant multiphoton absorption compound (particularly a non-resonant two-photon absorption compound), it is possible to form a high-definition recording mark without using a short wavelength laser, and deformation of the material in the light irradiation part. Induced light-stable recording marks were realized (so-called heat mode recording). In addition, by using a compound having a large two-photon absorption cross section among organic compounds capable of imparting desired physical properties by molecular design, it is possible to realize a highly sensitive optical information recording medium using two-photon absorption. The object of the present invention has been achieved by the following means.

(1) A recording method for an optical information recording medium having a recording component containing at least one non-resonant multiphoton absorption compound, wherein the recording component does not have linear absorption in a wavelength region from ultraviolet to near infrared And recording information by causing non-resonant multiphoton absorption and irradiating at least a part of the recording component of the irradiated portion.
(2) The deformation is induced by irradiating light having a wavelength longer than an absorption band existing on the longest wavelength side of the non-resonant multiphoton absorption compound and having no linear absorption of the compound. The optical information recording method according to (1).
(3) An optical information reading method, wherein information recorded by the optical information recording method according to (1) to (2) is read as a change in light reflectance or light transmittance.
(4) An optical information recording medium, wherein information is recorded using the optical information recording method described in (1) to (2).
(5) The optical information recording medium according to (4), wherein the non-resonant multiphoton absorption compound has a two-photon absorption cross section of 500 GM (1 GM = 10 ⁻⁵⁰ cm ⁴ s photon ⁻¹ ) or more.
(6) The optical information recording medium according to (4) or (5), wherein the multiphoton absorption compound is a transition metal complex compound.
(7) The optical information recording medium according to any one of (4) to (6), wherein information is recorded in three dimensions.
(8) In the transition metal complex compound according to (6), at least one of the coordination atoms coordinated to the transition metal ion is any one of a nitrogen atom, a sulfur atom, an oxygen atom, a carbon atom, a phosphorus atom, and a halogen atom. (6) The optical information recording medium according to (6).
(9) The optical information recording medium according to (6) or (7), wherein the transition metal complex compound contains at least one bidentate or more multidentate ligand.

  By using the optical recording method and the optical recording medium of the present invention, a high-density optical recording medium can be obtained without using a short wavelength laser light source.

The optical information recording method of the present invention will be described in detail below.
As the recording light used in the optical information recording method of the present invention, laser light in a wavelength region from the ultraviolet to the near infrared and a wavelength region in which no absorption of the recording medium exists is used. More preferably, it is a laser beam having a wavelength longer than the absorption band existing on the longest wavelength side of the optical recording medium and having no linear absorption of the recording medium.

  In the optical information recording method of the present invention, the recording medium has a recording component, and the recording component contains at least one non-resonant multiphoton absorption compound. When the recording medium is irradiated with laser light having the above wavelength, the recording component contained in the light irradiation portion causes non-resonant two-photon absorption and the light energy is absorbed. When a part of the recording component present in the light irradiation part is heated by the absorbed energy and the bonds between atoms are cleaved, dissolution, decomposition, evaporation, etc. occur, and the shape is deformed. The optical information recording method of the present invention is characterized in that information is recorded by forming a deformation of the recording component in the light irradiation section, and information is read out using a change in light reflectance and / or light transmittance due to the deformation. And

  In the present invention, the deformation of the recording component occurring in the light irradiation part is, for example, that the recording layer is melted or decomposed by heat and the substrate is softened, and a mixture of the recording layer material and the substrate material is formed at the interface between the substrate and the recording layer. Deformation of the recording layer and the substrate due to the formation, decomposition of the recording layer due to heat, and the degradation of the recording layer material remaining at the interface between the substrate and the recording layer, deformation of the recording layer and the substrate, The gas is decomposed to generate gas, and the recording layer is deformed due to the formation of voids in the recording layer. The recording layer is thermally decomposed to generate gas, and the gas pressure causes the recording layer and the reflective layer to be convex. This refers to deformation that changes, or deformation that occurs when the recording layer is decomposed by heat and the substrate is softened, and the shape of the substrate and the reflective layer is changed by the gas pressure generated by the decomposition of the recording layer.

  Next, the optical recording medium of the present invention will be described in detail. The optical information recording medium of the present invention records information by irradiating the laser beam having the above-mentioned wavelength and causing deformation of the recording component in the light irradiation portion, and changes in light reflectance and / or light transmittance due to the deformation. The optical recording medium is characterized in that information is read out using the.

In the optical information recording medium of the present invention, the organic compound contained in the recording component is not particularly limited, but an organic compound having a two-photon absorption cross section of 500 GM (1 GM = 10 ⁻⁵⁰ cm ^{4 s} photon ⁻¹ ) or more ( At least one multiphoton absorbing compound) is included. The multiphoton absorption compound is preferably a two-photon absorption compound, more preferably an organic compound having a two-photon absorption cross section of 1000 GM or more, and more preferably a two-photon absorption cross section of 2000 GM or more. It is an organic compound having

Examples of the two-photon absorption compound include dye compounds as shown below.
For example, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, Squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, xanthene dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, Phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine Down dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes.

  Preferably, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, oxonol dye, squalium dye, arylidene dye, triphenylmethane dye, xanthene dye, azo Dyes, porphyrin dyes, and more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, oxonol dyes, squalium dyes, arylidene dyes, etc. An azo dye, a methine dye, and a phthalocyanine dye, and more preferably a cyanine dye, a merocyanine dye, an oxonol dye, an azo dye, or a phthalocyanine dye. Ri, and most preferred are cyanine dyes, oxonol dyes, azo dyes or phthalocyanine dyes.

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

  The general formulas of cyanine dye and merocyanine dye are those shown in (XI) and (XII) on pages 21 and 22 of US Pat. No. 5,340,694 (however, the number of n12 and n15 is not limited and is an integer of 0 or more) (Preferably an integer of 0 to 4)).

  When the two-photon absorption compound of the present invention is a cyanine dye, it is preferably represented by the following general formula (1).

In the general formula (1), Za ₁ and Za ₂ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle. The 5-membered or 6-membered nitrogen-containing heterocycle formed is preferably an oxazole nucleus having 3 to 25 carbon atoms (hereinafter referred to as C number) (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl). , 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropyl Benzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- ( -Naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2- 3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3 -Dimethyl-5,6-dimethylthiobenzoxazolyl), thiazole nuclei having 3 to 25 carbon atoms (for example, 2-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2- 3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2 -3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl , 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro -3-methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl 2-5-phenyl-3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6- Dimethylthiobenzothiazolyl), imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2- 1,3,4-triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro- 1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl, etc.), C10-30 indolenine nucleus (for example, 3,3-dimethylindolenine) ), A quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl) 2-1-methyl 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1 And sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.) , A C 3-25 selenazole nucleus (for example, 2-3methylbenzoselenazolyl etc.), a C 5-25 pyridine nucleus (for example, 2-pyridyl etc.) and the like can be mentioned. In addition, thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quino Zarin] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, may be mentioned pyrimidine nucleus.

  These may be substituted, and the substituent is preferably, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3- Sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, for example cyclopentyl, cyclohexyl), aryl groups (preferably C 6-20, for example phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic groups ( Preferably C number 1-20, for example pyridyl, thienyl, furyl, thiazolyl, imida Yl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (for example, F, Cl Br, I), amino group (preferably C 0-20, for example, amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, Phosphonic acid group, acyl group (preferably C 1-20, such as acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C 1-20, such as methoxy, butoxy, cyclohexyloxy), aryloxy group (Preferably C number 6-26, for example, phenoxy, 1 Naphthoxy), alkylthio group (preferably C number 1-20, for example, methylthio, ethylthio), arylthio group (preferably C number 6-20, for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably C number) 1-20, such as methanesulfonyl, butanesulfonyl), arylsulfonyl groups (preferably C6-6, such as benzenesulfonyl, paratoluenesulfonyl), sulfamoyl groups (preferably C0-20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (Preferably C number 1 -20, such as acetylamino, benzoylamino), imino group (preferably C 2-20, such as phthalimino), acyloxy group (preferably C 1-20, such as acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably Is a C 2-20, such as methoxycarbonyl, phenoxycarbonyl), or a carbamoylamino group (preferably a C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), and more An alkyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group is preferable.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

More preferably, the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Za ₁ and Za ₂ is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, and more preferably an oxazole nucleus, an imidazole nucleus, or An indolenine ring, most preferably an oxazole nucleus or an indolenine nucleus.

Ra ₁ and Ra ₂ are each independently a hydrogen atom or an alkyl group (preferably having a C number of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl. , 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl), aryl group ( Preferably C6-20, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), or a heterocyclic group (preferably C1-20, such as pyridyl, thienyl, Furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably Alkyl group (preferably an alkyl group having a C number of 1 to 6) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl) is.

Ma ^{1 to} Ma ⁷ each represent a methine group and may have a substituent (examples of preferred substituents are the same as examples of substituents on Za ₁ and Za ₂ ), and preferably an alkyl group as a substituent , Halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. More preferably, it is an alkyl group.
Ma ^{1 to} Ma ⁷ are preferably an unsubstituted methine group or an alkyl group (preferably having a C number of 1 to 6) substituted methine group, more preferably an unsubstituted, ethyl group-substituted, or methyl group-substituted methine group.
Ma ^{1 to} Ma ⁷ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

na ¹ and na ² is 0 or 1, preferably both 0.

ka ¹ represents an integer of 0 to 3, more preferably ka ¹ represents ¹ to 3, and further preferably ka ¹ represents 1 or 2.
When ka ¹ is 2 or more, a plurality of Ma ₃ and Ma ₄ may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is a merocyanine dye, it is preferably represented by the following general formula (2).

In the general formula (2), Za ₃ represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle (preferred examples are the same as Za ₁ and Za ₂ ), and these may be substituted (preferred substitution) examples of groups are the same as examples of the substituent on Za1, Za _2)), these heterocyclic rings may be further condensed with another ring.

The 5-membered or 6-membered nitrogen-containing heterocycle formed by Za ₃ is more preferably an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine nucleus, and more preferably an oxazole nucleus or an indolenine nucleus.

Za ₄ represents an atomic group forming a 5-membered or 6-membered ring. The ring formed from Za ₄ is a part generally called an acidic nucleus, and is defined by James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198. Za ₄ is preferably 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline- 5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one Indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3 -Dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazolin-2-one, pyri Examples include nuclei such as do [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, and pyrazolopyridone.
More preferably, the ring formed from Za ₄ is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one- 1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, or coumarin-2,4-dione, more preferably pyrazolidine-3,5-dione Indane-1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, or 2-thiobarbituric acid, most preferably pyrazolidine-3,5-dione, barbituric acid, Or 2-thiobarbituric acid.

The ring formed from Za ₄ may be substituted (preferred examples of the substituent are the same as the examples of the substituent on Za ₃ ). More preferably, the substituent is preferably an alkyl group, aryl group, heterocyclic group, halogen An atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

Ra ₃ is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra ₁ and Ra ₂ ), more preferably an alkyl group (preferably having a C number of 1 to 6 alkyl group) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl).

Ma ^{8 to} Ma ¹¹ each represent a methine group and may have a substituent (examples of preferred substituents are the same as examples of substituents on Za ₁ and Za ₂ ), and preferably an alkyl group as a substituent , Halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. More preferably, it is an alkyl group.
Ma ^{8 to} Ma ¹¹ are preferably an unsubstituted methine group or an alkyl group (preferably having a C number of 1 to 6) substituted methine group, more preferably an unsubstituted, ethyl group-substituted, or methyl group-substituted methine group.
Ma ^{8 to} Ma ¹¹ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

na ³ is 0 or 1, preferably 0.

ka ² represents an integer of 0 to 8, preferably an integer of 0 to 4, more preferably an integer of 2 to 4.
When ka ² is 2 or more, the plurality of Ma ¹⁰ and Ma ¹¹ may be the same or different.

  CI represents an ion that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is an oxonol dye, it is preferably represented by the general formula (3).

In general formula (3), Za ₅ and Za ₆ each represent an atomic group forming a 5-membered or 6-membered ring (preferred examples are the same as Za ₄ ), and these may be substituted (examples of preferred substituents). Is the same as the example of the substituent on Za ₄ ), and these heterocyclic rings may be further condensed.
More preferably, the ring formed from Za ₅ and Za ₆ is more preferably 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophene-3. -One-1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, meldrum acid, coumarin-2,4-dione, more preferably barbituric acid 2-thiobarbituric acid or meldramic acid, most preferably barbituric acid or meldramic acid.

Ma ^{12 to} Ma ¹⁴ each represent a methine group and may have a substituent (preferred examples of the substituent are the same as the examples of the substituent on Za ₅ and Za ₆ ), and the substituent is preferably alkyl. Group, halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. An alkyl group, a halogen atom, an alkoxy group, an aryl group, a heterocyclic group, a carbamoyl group, or a carboxy group is more preferable, and an alkyl group, an aryl group, or a heterocyclic group is more preferable.
Ma ^{12 to} Ma ¹⁴ are preferably unsubstituted methine groups.
Ma ^{12 to} Ma ¹⁴ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

ka ³ represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 1 or 2, and most preferably 2.
When ka ³ is 2 or more, Ma ¹² and Ma ¹³ may be the same or different.

  CI represents an ion that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is an azo dye, it is preferably represented by the general formula (4).

In the general formula (4), A ₁ represents a residue which forms a 5-membered or 6-membered heterocyclic ring together with the carbon atom and nitrogen atom to which it is bonded, preferably A ₁ is Is preferably a residue which together with the carbon and nitrogen atoms to which is bonded forms a heterocycle selected from the group consisting of thiadiazole, isoxazole, imidazole, pyrazole, thiazole, triazole, pyridine, In general formula (4)

The following may be mentioned.

In the formula, D _{1 to} D ₃₃ are each independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as an n-hexyl group; a cyclic alkyl group having 3 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group; a methoxy group, an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group; acetyl group, propiol Group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, heptanoyl group, etc. Alkyl carbonyl groups; linear or branched alkenyl groups having 2 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group, pentenyl group and hexenyl group; and having 3 to 6 carbon atoms such as cyclopentenyl group and cyclohexenyl group Cyclic alkenyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom; formyl group; hydroxyl group; carboxyl group; hydroxyalkyl group having 1 to 6 carbon atoms such as hydroxymethyl group, hydroxyethyl group; methoxycarbonyl group, ethoxy Carbon number such as carbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc. ~ 7 alkoxycarboni Group: nitro group; cyano group; amino group; methylamino group, ethylamino group, n-propylamino group, n-butylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n- An alkylamino group having 1 to 10 carbon atoms such as a butylamino group; an alkoxycarbonylalkyl group having 3 to 7 carbon atoms such as a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, and an isopropoxycarbonylethyl group; An alkylthio group having 1 to 6 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, tert-butylthio group, sec-butylthio group, n-pentylthio group, n-hexylthio group; methylsulfonyl group, ethylsulfonyl group, n -Propylsulfonyl group, isopropylsulfonyl group, n-butyl An alkylsulfonyl group having 1 to 6 carbon atoms such as tilsulfonyl group, tert-butylsulfonyl group, sec-butylsulfonyl group, n-pentylsulfonyl group and n-hexylsulfonyl group; An aryl group having 6 to 16 carbon atoms; an arylcarbonyl group having 7 to 17 carbon atoms which may have a substituent; —CD ₃₄ ═C (CN) D ₃₅ (D ₃₄ is a hydrogen atom or a methyl group, an ethyl group, n - propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, n- pentyl group, an alkyl group having 1 to 6 carbon atoms, such as n- hexyl group, D ₃₅ is a cyano group or Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxy It represents a carbonyl group, sec- butoxycarbonyl group, n- pentyl group, an alkoxy group having 2 to 7 carbon atoms such as n- hexyloxy carbonyl group. );

(D ₃₆ to D ₃₈ are each independently a hydrogen atom, a nitro group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec -C1-C6 linear or branched alkyl groups such as butyl, tert-butyl, n-pentyl, and n-hexyl; carbon numbers such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl 3 to 6 cyclic alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group Represents an alkoxy group having 1 to 6 carbon atoms, such as

(D ₃₉ to D ₄₁ are each independently a hydrogen atom, a nitro group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec -C1-C6 linear or branched alkyl groups such as butyl, tert-butyl, n-pentyl, and n-hexyl; carbon numbers such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl 3 to 6 cyclic alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group represents a 6 alkoxy group having a carbon number of 1 etc., L represents a SCH _2, SO _2);. a trifluoromethyl group, pentafluoroethyl , Heptafluoro-n-propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoro-sec-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, etc. -6 fluoroalkyl group; trifluoromethoxy group, pentafluoroethoxy group, trifluoroethoxy group, pentafluoroethoxy group, perfluoro-n-butoxy group, perfluoro-tert-butoxy group, perfluoro-sec-butoxy group , Perfluoro-n-pentyloxy group, perfluoro-n-hexyloxy group, etc., a fluoroalkoxy group having 1 to 6 carbon atoms; trifluoromethylthio group, trifluoroethylthio group, pentafluoroethylthio group, heptafluoro-n -Propylthio group, heptafluoroiso Fluoro having 1 to 6 carbon atoms such as propylthio group, perfluoro-n-butylthio group, perfluoro-t-butylthio group, perfluoro-sec-butylthio group, perfluoro-n-pentylthio group, perfluoro-n-hexylthio group Represents an alkylthio group or the like;

In the general formula (4), R ₂₁ and R ₂₂ are each independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group. A linear or branched alkyl group having 1 to 20 carbon atoms such as n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, etc. , Preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Such a linear or branched alkyl group having 1 to 20 carbon atoms is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a sec-butoxy group, or an n-pentyloxy group. , An n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-decyloxy group, etc., an alkoxy group having 1 to 10 carbon atoms; a methoxymethoxy group, an ethoxymethoxy group, a propoxymethoxy group, a methoxyethoxy group, C2-C12 alkoxyalkoxy groups such as ethoxyethoxy group, propoxyethoxy group, methoxypropoxy group, ethoxypropoxy group, methoxybutoxy group, ethoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, Methoxyethoxyethoxy , Alkoxy group having 3 to 15 carbon atoms such as ethoxymethoxymethoxy group, ethoxymethoxyethoxy group, ethoxyethoxymethoxy group, ethoxyethoxyethoxy group; allyloxy group; carbon such as phenyl group, tolyl group, xylyl group, naphthyl group An aryl group having 6 to 12 carbon atoms; an aryloxy group having 6 to 12 carbon atoms such as a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group; a cyano group; a nitro group; a hydroxy group; a tetrahydrofuryl group; Ethylsulfonylamino group, n-propylsulfonylamino group, isopropylsulfonylamino group, n-butylsulfonylamino group, tert-butylsulfonylamino group, sec-butylsulfonylamino group, n-pentylsulfonylamino group, An alkylsulfonylamino group having 1 to 6 carbon atoms such as a hexylsulfonylamino group; a halogen group such as a fluorine atom, a chlorine atom or a bromine atom; a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group; an alkoxycarbonyl group having 2 to 7 carbon atoms such as n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group; methylcarbonyloxy group, ethylcarbonyl Oxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, tert-butylcarbonyloxy group, sec-butylcarbonyloxy group, n-pentylcarbonyloxy group; n-he C2-C7 alkylcarbonyloxy group such as xylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, tert-butoxy It may be substituted with a C2-C7 alkoxycarbonyloxy group such as a carbonyloxy group, a sec-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, or an n-hexyloxycarbonyloxy group. Alternatively, R ₂₁ and R ₂₂ represent a residue that forms a ring, preferably a 5- or 6-membered ring. Further, R ₂₁ and X may combine to form a ring, preferably a 5- or 6-membered ring.

X may include a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and particularly preferably a hydrogen atom or a methoxy group. Y is a linear or branched alkyl group having 1 to 6 carbon atoms in which at least two (preferably three or more) are substituted with fluorine atoms. Specifically, C1-C6 perfluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl, etc. Examples thereof include an alkyl group substituted with a perfluoroalkyl group having 2 to 6 carbon atoms in total such as a group, 2,2,3,3,3-pentafluoropropyl group, and the like. Particularly preferred is —CH ₂ CF ₃ or —CF ₃ .

  Of the azo compounds, compounds represented by the following general formulas (4-1) to (4-9) are more preferable.

In the general formulas (4-1) to (4-9), Xa represents a hydrogen atom, a methoxy group, an ethoxy group, or a propoxy group, and Y represents 1 to 6 carbon atoms substituted with at least two fluorine atoms. R ₁₀₁ , R ₁₀₂ and R ₁₀₃ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and R ₁₀₄ , R ₁₀₅ each independently represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, a cyano group, or a carboxylic acid ester group, and R ₁₀₆ has a substituent. And may represent a linear or branched alkyl group, alkoxy group, or alkylthio group having 1 to 6 carbon atoms. R ₁₀₇ to R ₁₁₀ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, represents a hydrogen atom or a halogen atom.

  The azo dye of the present invention is also preferably one represented by the following general formula (5).

In the general formula (5), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a substituent. Specific examples thereof include those described later in the description of R ⁵ and R ⁶ . Among them, preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aminocarbonyl group. Represents a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryloxycarboxyl group. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. R ¹ and R ² , and R ³ and R ⁴ may be bonded to each other to form a ring structure.
R ¹ , R ² , R ³ and R ⁴ are preferably an alkyl group (a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-hexyl). , I-propyl, t-butyl, n-octyl, n-octadecyl, 2-methoxyethyl, 3-chloropropyl), aryl group (C6-C20 substituted or unsubstituted aryl group such as phenyl, naphthyl) , P-methoxyphenyl, m-chlorophenyl, p-diethylaminophenyl), or a heterocyclic group (a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, for example, 2-pyridyl, 2-furyl). It is preferable that either one of R ¹ and R ² or R ³ and R ⁴ is a hydrogen atom and the other is not a hydrogen atom.
More preferably, either R ¹ or R ² is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the other is a hydrogen atom. Preferably there is. Either R ³ or R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the other is preferably a hydrogen atom. .

R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent. Substituents are halogen atoms, alkyl groups (including cycloalkyl groups and bicycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups , Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Famoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphine group Examples include a finyloxy group, a phosphinylamino group, and a silyl group.
More specifically, R ⁵ and R ^{6 each} represent a halogen atom (for example, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy (Preferably, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably carbon A substituted or unsubstituted aryloxy group of formula 6 to 30, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably, A silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy ), An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N , N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a group having 2 to 30 carbon atoms). Substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy groups (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonyloxy group of, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or non-substituted with 1 to 30 carbon atoms) Substituted alkylamino groups, substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino Group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino , Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoyl Amino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms) , For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms substituted or An unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably substituted with 0 to 30 carbon atoms or Unsubstituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably Or substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3, 5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (Preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) F Borocyclic thio group such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfa Moyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl P-methylphenyls Finyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl) P-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon number 4 To heterocyclic groups bonded to a carbonyl group by 30 to 30 substituted or unsubstituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Carbonyl, 2-furyl Rubonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxy Carbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably C1-C30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfo Nyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p- Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl) , Diethoxyphosphinyl), phosphinyl A xy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably carbon A substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms) Groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.
R ⁵ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aminocarbonyl group having 3 to 20 carbon atoms. , A carboxyl group, or a cyano group.
R ⁶ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. More preferably, it is a C1-C6 unsubstituted alkyl group.
B represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group that can be derived from a diazonium salt. That is, B is a diazo component. The diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent or a benzene derivative into a diazo compound (diazonium salt) and diazo coupling reaction with a coupler. It is a frequently used concept in the field. In other words, it is an amino-substituted heterocyclic compound capable of diazotization reaction or a substituent that is a monovalent group by removing the amino group of the benzene derivative.

  Examples of the monovalent heterocyclic group include the following (A-1) to (A-25).

In the formula, R ^{21 to} R ⁵⁰ are each independently a hydrogen atom or a substituent. Examples of the substituent are those described in the description of R ⁵ and R ⁶ .
b and c are each independently an integer of 0 to 6.
a, p, q, and r are each independently an integer of 0 to 4.
d, e, f, g, t, and u are each independently an integer of 0 to 3.
h, i, j, k, l, and o are each independently an integer of 0 to 2.
When a to u are 2 or more, two or more substituents represented by R ^{21 to} R ⁵⁰ may be the same or different.

  Among the structures of B, the following structures (a) -1, (a) -2, and (b) to (l) are preferable.

In the formula, R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁷¹ , R ⁷² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are each independently a hydrogen atom, Alternatively, it represents a substituent. Examples of the substituent include those described in the above description of R ⁵ and R ⁶ .

  The azo compound represented by the general formula (5) of the present invention is preferably represented by the following general formula (6).

In general formula (6), R ^1a , R ^2a and R ^3a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Represents. Examples of R ^1a , R ^2a , and R ^3a include the same examples and preferred examples as the alkyl group, aryl group, and heterocyclic group described in the above R ¹ to R ⁴ . R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent, and have the same meanings as R ⁵ and R ⁶ in formula (5). B ′ represents a group having a structure selected from the above formulas (a) -1, (a) -2, and (b) to (l).
In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ are each independently R ⁶⁶ , R ⁷¹ , R ⁷² are hydrogen atoms, Or a substituent is represented.
Among them, R ^1a , R ^2a and R ^3a are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ⁵ is an alkyl group. R ⁶ is preferably a hydrogen atom, a carboxyl group, a cyano group, or an aminocarbonyl group, and B ′ is preferably a compound of the formula (f), (a) -2, or (a) -1.

As the two-photon absorption compound, a transition metal complex compound is also preferable. As the transition metal complex compound, a ligand in which the coordination atom coordinated to the transition metal ion is any one of a nitrogen atom, a sulfur atom, an oxygen atom, a carbon atom, a phosphorus atom, and a halogen atom is coordinated A transition metal compound having a structure is preferable.
The transition metal complex compound is preferably a transition metal complex compound coordinated with a bidentate or more multidentate ligand, more preferably a transition metal complex compound coordinated with a tridentate or tetradentate ligand. It is.

Specific examples of the transition metal compound include the following compounds. Metal porphyrin complexes, metal azaporphyrin complexes, phthalocyanine complexes, and azo metal complexes in which the azo dye is coordinated to a metal ion.
Preferred are metal azaporphyrin complexes, phthalocyanine complexes and azo metal complexes, and more preferred are phthalocyanine complexes and azo metal complexes.

  When the two-photon absorption compound (the transition metal complex compound) of the present invention is a metal azaporphyrin complex, it is preferably represented by the following general formula (7).

In the general formula (7), R _{1 to} R ₈ each independently represent a hydrogen atom or a substituent, and the substituent is preferably, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n- Propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl, 2 -Butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, such as cyclopentyl, cyclohexyl), aryl group (preferably C 6-20, such as phenyl, 2-chlorophenyl, 4-methoxy Phenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, for example, phenyl Diyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), an alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), Halogen atom (eg, F, Cl, Br, I), amino group (preferably C 0-20, eg, amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto Group, carboxyl group, sulfo group, phosphonic acid group, acyl group (preferably C number 1-20, for example, acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C number 1-20, for example, methoxy, butoxy Cyclohexyloxy), aryloxy group (preferred Or C6-C26, such as phenoxy, 1-naphthoxy), alkylthio group (preferably C1-20, such as methylthio, ethylthio), arylthio group (preferably C6-C20, such as phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (preferably C 1-20, such as methanesulfonyl, butanesulfonyl), an arylsulfonyl group (preferably C6-20, such as benzenesulfonyl, paratoluenesulfonyl), Sulfamoyl group (preferably C 0-20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably C 1-20, such as carbamoyl, N-methylcarbamoyl, N N-dimethylcarbamoyl, N-phenylcal Moyl), acylamino groups (preferably C 1-20, such as acetylamino, benzoylamino), imino groups (preferably C 2-20, such as phthalimino), acyloxy groups (preferably C1-20, such as acetyl) Oxy, benzoyloxy), alkoxycarbonyl group (preferably C 2-20, such as methoxycarbonyl, phenoxycarbonyl), or carbamoylamino group (preferably C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), more preferably alkyl group, aryl group, heterocyclic group, halogen atom, cyano group, nitro group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, Aryl sul Group, a sulfamoyl group, a carbamoyl group, an acyloxy group or an alkoxycarbonyl group.

In the general formula (7), M represents a metal ion, preferably a transition metal metal ion. Specifically preferably represents titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, palladium, platinum, gold, magnesium, aluminum, zinc or silicon, more preferably copper, nickel, palladium or silicon. Most preferably, it is copper.
In addition, a ligand (preferably, for example, pyridines which may be substituted and imidazoles which may be substituted are coordinated to zinc, copper, iron, cobalt, etc.) is coordinated on the metal atom. Or a substituent may be covalently bonded (preferably, for example, two alkoxy groups or chloro groups are substituted on silicon).

In the general formula (7), R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₅ , R ₇ and R ₈ may be connected to each other to form a ring, R ₁ and R ₂ , R More preferably, ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ are all connected to each other to form a ring.
A ring formed at that time is preferably a benzene ring, a pyridine ring, a pyrazine ring, a naphthalene ring, an anthracene ring or a phentolen ring.

  The azaporphyrin dye represented by the general formula (7) in the present invention is more preferably a phthalocyanine complex represented by the general formula (8).

In the general formula (8), Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} β ⁸ each independently represent a hydrogen atom or a substituent (preferred examples of the substituent are the same as those of R _{1 to} R ₈ ), preferably an alkyl group, Aryl group, heterocyclic group, halogen atom, cyano group, nitro group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carbamoyl group, acyloxy group, or alkoxycarbonyl group It is.

Further, Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} β ⁸ are preferably a hydrogen atom or an electron withdrawing group, and the electron withdrawing group indicates that the σp value in the Hammett equation takes a positive value. Preferably trifluoromethyl group, heterocyclic group, halogen atom, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carbamoyl group, acyloxy group, alkoxycarbonyl group, etc. A trifluoromethyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group, and most preferably an alkylsulfonyl group.

Furthermore, in general formula (8), it is more preferable that Rβ ^{1 to} β ⁸ are all hydrogen atoms, and Rα ^{1 to} Rα ⁸ are each independently a hydrogen atom or an electron withdrawing group.

Adjacent Rα ¹ to Rα ⁸ and Rβ ^{1 to} β ⁸ may be connected to each other to form a ring, and the ring to be formed is preferably a benzene ring, a naphthalene ring, a pyridine ring, or a pyrimidine ring.

  In the general formula (8), M is synonymous with the general formula (7).

  The azaporphyrin dye and phthalocyanine dye of the present invention may be bonded at an arbitrary position to form a multimer. In this case, each unit may be the same as or different from each other, and polystyrene, polymethacrylate, polyvinyl alcohol Or may be bonded to a polymer chain such as cellulose.

  The azaporphyrin dye and phthalocyanine dye of the present invention may be used alone as a specific derivative, or may be used by mixing a plurality of types having different structures. Moreover, you may use the mixture of the isomer from which the substitution position of a substituent differs.

  When the two-photon absorption compound of the present invention is a metal azo complex, preferably a metal azo in which at least one of the azo dyes represented by the general formulas (4) to (6) is coordinated to a metal ion as a ligand. It is a complex.

  In the azo metal complex of the present invention, the metal ion to which the azo dye represented by the general formulas (4) to (6) coordinates as a ligand is not particularly limited, but is preferably a transition metal metal ion. . Specifically preferred are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper or zinc, more preferred are copper, cobalt and nickel, and most preferred is nickel.

  Specific examples of the two-photon absorption compound used in the present invention are listed below, but the present invention is not limited thereto.

D-170 D-134 Ni chelate D-171 D-135 Zinc chelate D-172 D-138 Ni chelate D-173 D-141 Ni chelate D-174 D-151 Zinc chelate D-175 D- 154 copper chelate D-176 D-164 Ni chelate D-177 D-164 Ti chelate D-178 D-164 zinc chelate

  Moreover, although the preferable example of the azo compound of this invention other than General formula (1), (3) is given to the following, this invention is not limited to this.

The notation Rα ¹ / Rα ² represents the meaning of either Rα ¹ or Rα ² , and therefore a compound having this notation is a mixture of substitutional position isomers. In the case of no substitution, that is, when a hydrogen atom is substituted, the notation is omitted.

  Next, the structure of the optical information recording medium of the present invention will be described. The optical information recording medium of the present invention is not particularly limited as long as it contains a non-resonant multiphoton absorption compound (preferably a two-photon absorption compound represented by the general formulas (1) to (8)). For a recording (planar recording) medium, a recording layer containing the two-photon absorption compound is preferably formed on a substrate in a thin film form. For a three-dimensional recording (stereoscopic recording) medium, the multiphoton absorption compound is used as a polymer matrix. A block shape dispersed therein is preferred. The optical information recording medium of the present invention is more preferably a three-dimensional recording medium.

  In the case of a recording medium in which the recording layer containing the two-photon absorption compound is formed in a thin film on a substrate, a thickness of 0.1 to 0.1 mm on which pregrooves (for example, a track pitch of 0.1 to 2.0 μm) are formed. A configuration in which a recording layer containing a compound represented by the general formulas (1) to (8) is provided on a 3 mm transparent disk-shaped substrate can be preferably used. Moreover, the pre-groove may or may not be present.

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

  When there is a pre-groove on the substrate (or undercoat layer), it is an unevenness (pre-groove) representing information such as a tracking groove or an address signal, and directly when a resin material such as polycarbonate is injection molded or extruded. It is preferably formed on the substrate at the track pitch described above. Further, the pregroove may be formed by providing a pregroove layer. As a material of the pregroove layer, a mixture of at least one monomer (or oligomer) of monoester, diester, triester and tetraester of acrylic acid and a photopolymerization initiator can be used. For example, the pregroove layer is formed by, first, applying a liquid mixture comprising the above acrylate ester and a polymerization initiator on a precisely formed master (stamper), and further placing a substrate on the coating liquid layer. After that, the coating layer is cured by irradiating ultraviolet rays through the substrate or the mother die, and the substrate and the coating layer are fixed. Subsequently, it can obtain by peeling a board | substrate from a mother mold. The thickness of the pregroove layer is in the range of 0.05 to 100 μm, preferably in the range of 0.1 to 50 μm.

  A recording layer containing the two-photon absorption compound represented by the above formula according to the present invention is provided on the substrate (or undercoat layer) or on the surface where the pregroove is formed. As a method for forming the recording layer, a vacuum deposition method, a coating method, or the like can be used. Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The thickness of the recording layer can generally be in the range of 20 nm to 0.1 mm, and preferably in the range of 50 nm to 1 μm. Furthermore, multilayer recording is possible by controlling the focal depth of the laser beam, and in this case, a thicker recording layer can be obtained. Thereby, higher density recording can be made possible.

  The recording layer is formed by a coating method by preparing a coating solution by dissolving the two-photon absorption compound according to the present invention and, if desired, a binder in a solvent, and then coating the coating solution on the substrate surface. It can be performed by forming and then drying. Examples of the solvent for the coating solution for forming the recording layer include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform. Amides such as dimethylformamide; hydrocarbons such as cyclohexane; ethers such as tetrahydrofuran, ethyl ether, dioxane; alcohols such as ethanol, n-propanol, isopropanol, n-butanol, diacetone alcohol; 2, 2, 3, Fluorinated solvents such as 3-tetrafluoropropanol; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether Or the like can be mentioned ether compounds. The said solvent can be used individually or in combination of 2 or more types in consideration of the solubility of the compound to be used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution depending on the purpose.

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

  In order to further improve the light resistance of the recording layer, the recording layer can contain various anti-fading agents. Examples of the antifading agent include organic oxidants, singlet oxygen quenchers, tetracyanoquinodimethane (TCNQ) derivatives, and 4,4'-bipyridyl derivatives. In addition, when the two-photon absorption compound has a charge, a two-photon absorption compound-antifading agent versus salt compound that is salified with an anti-fading agent having a charge opposite to that of the two-photon absorption compound is used. You can also.

  An undercoat layer may be provided on the surface of the substrate on which the recording layer is provided for the purpose of improving the flatness, improving the adhesive force, and preventing the recording layer from being altered. Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfonated. High molecular substances such as polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; and silane coupling agents And the like.

  A light reflecting layer may be provided on the recording layer for the purpose of improving the reflectance during information reproduction. The light-reflecting substance that is the material of the light-reflecting layer is a substance having a high reflectance with respect to laser light. Examples thereof include 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, Mention may be made of metals such as Bi and metalloids or stainless steel. Of these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable, and Ag is particularly preferable. These substances may be used alone or in combination of two or more or as an alloy. The light reflecting layer can be formed on the recording layer, for example, by vapor deposition, sputtering or ion plating of the reflective material. The layer thickness of the light reflecting layer can generally be in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.

A protective layer may be provided on the light reflecting layer for the purpose of physically and chemically protecting the recording layer and the like. This protective layer may be provided on the side where the base recording layer is not provided for the purpose of improving scratch resistance and moisture resistance. Examples of the material used for the protective layer include inorganic substances such as SiO, SiO ₂ , MgF ₂ , SnO ₂ , and Si ₃ N _4, and organic substances such as thermoplastic resins, thermosetting resins, and UV curable resins. be able to. The protective layer can be formed, for example, by laminating a film obtained by extrusion of plastic on the light reflecting layer and / or the substrate. Or you may provide by methods, such as vacuum evaporation, sputtering, and application | coating. In the case of a thermoplastic resin or a thermosetting resin, it can also be formed by preparing a coating solution by dissolving it in an appropriate solvent and then applying and drying the coating solution. In the case of a UV curable resin, it can also be formed by preparing a coating solution as it is or by dissolving it in a suitable solvent, coating the coating solution, and curing it by irradiating with UV light. In these coating liquids, various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added according to the purpose. The thickness of the protective layer can generally be in the range of 0.1 to 100 μm.

  When the optical information recording medium of the present invention is in the form of a block in which the two-photon absorption compounds represented by the general formulas (1) to (8) are dispersed in a polymer matrix, three-dimensional recording is possible. In this case, the polymer matrix in which the two-photon absorption compound is dispersed is not particularly limited. For example, an acrylic resin such as polycarbonate or polymethyl methacrylate, an epoxy resin, an amorphous polyolefin, a polyester, a vinyl chloride resin, or polyethylene terephthalate is used. be able to.

  The two-photon absorption compound contained in the polymer matrix needs to be contained in a proportion of 1 to 90% by mass, and is preferably contained in a proportion of 5 to 80% by mass. The shape of the block is not particularly limited, and it may be a disk-like and thick shape, a cube or a rectangular parallelepiped, but a disk-like and thick shape is preferable.

  The method for dispersing the two-photon absorption compound in the polymer matrix is not particularly limited, and various methods can be used. For example, a polymer compound is dissolved, and the two-photon absorption compound is added thereto and mixed uniformly, and then allowed to cool, or the polymer compound and the two-photon absorption compound are dissolved in a suitable solvent and heated. Examples thereof include a method of evaporating the solvent, or a method of dissolving the two-photon absorption compound in a corresponding monomer and polymerizing it by a polymerization reaction.

  When the optical information recording medium of the present invention is a three-dimensional recording medium, it is preferable to have a three-dimensional structure in which each information is recorded in a plane and the recording surfaces are stacked in multiple layers. Each layer of the three-dimensional recording medium preferably has position information (address signal) representing a relative or absolute positional relationship between the layers.

As the recording light source, laser light having a wavelength longer than the linear absorption band of the two-photon absorption compound and having no linear absorption is used. Specifically, a solid-state laser or a fiber laser having an oscillation wavelength of 700 to 1100 nm, a semiconductor laser or a solid-state laser having an oscillation wavelength near a central wavelength of 780 nm, a semiconductor laser or a solid-state laser having an oscillation wavelength of 620 to 680 nm, or a 400 to 480 nm A semiconductor laser or a solid-state laser having an oscillation wavelength can be used. It is also preferable to record a signal by irradiating a recording laser such as a semiconductor laser from the substrate side while rotating the optical recording medium of the present invention at a constant linear velocity or a constant angular velocity, for example.
[Example]
Hereinafter, specific examples of the present invention will be described based on experimental results. Of course, the present invention is not limited to these examples.

Experimental Example 1: Evaluation of two-photon absorption cross-section The evaluation of the two-photon absorption cross-section of the two-photon absorption compound of the present invention is based on the fluorescence method when the compound is fluorescent and when the compound is non-fluorescent. Was performed using the Z-Scan method.
<Fluorescence method>
The two-photon absorption cross section is evaluated by the fluorescence method. A. Albota et al. , Appl. Opt. 1998, 37, 7352. The description was made with reference to the method described. This measurement method is a method for comparing the intensity of light emission from an excited state induced by non-resonant two-photon absorption between a reference substance and a substance to be measured, and must be a compound that causes two-photon emission. Although it cannot be measured, it is characterized in that a simpler and relatively accurate value can be obtained as compared with other methods. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for measuring the two-photon absorption cross section, and two-photon absorption is performed in a wavelength range of 700 nm to 1000 nm. The cross-sectional area was measured. In addition, rhodamine B and fluorescein were measured as reference substances, and the obtained measured values were calculated as C.I. Xu et al. , J .; Opt. Soc. Am. B 1996, 13, 481. Were corrected using the values of the two-photon absorption cross sections of rhodamine B and fluorescein described in 1. to obtain the two-photon absorption cross sections of the respective compounds. As a sample for two-photon absorption measurement, a solution in which a compound was dissolved in chloroform or DMSO at a concentration of 1 × 10 ⁻³ was used.
<Z-Scan method>
The evaluation of the two-photon absorption cross section by the Z-Scan method is described in MANSOOR SHEIK-BAHAE et al. , IEEE. Journal of Quantum Electronics. 1990, 26, 760. The Z scan method described was used. The Z-scan method is widely used as a method for measuring nonlinear optical constants. The measurement sample is moved along the beam near the focal point of the focused laser beam, and the change in the amount of transmitted light is recorded. . Since the power density of incident light varies depending on the position of the sample, the amount of transmitted light attenuates near the focal point when there is nonlinear absorption. A two-photon absorption cross-sectional area was calculated by fitting a change in the amount of transmitted light with respect to a theoretical curve predicted from incident light intensity, focused spot size, sample thickness, sample concentration, and the like. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for measuring the two-photon absorption cross section, and two-photon absorption is performed in a wavelength range of 700 nm to 1000 nm. The cross-sectional area was measured. As a sample for two-photon absorption measurement, a solution in which a compound was dissolved in chloroform at a concentration of 1 × 10 ⁻³ was used.

  Table 2 shows the two-photon absorption cross-sectional area of the two-photon absorption compound of the present invention evaluated by the above method.

  Experimental example 2

Production of optical recording media (1)
1 g of the two-photon absorption compound (D-94) was dissolved in 100 ml of tetrafluoropropanol to obtain a recording layer forming coating solution. This coating solution was applied to a glass substrate by a spin coating method to produce an optical recording medium on which a coating film having a thickness of about 100 nm was formed.
An optical recording medium was prepared in the same manner as described above except that D-102-2, D-109, D-110 and D-212 were used instead of D-94 as the two-photon absorption compound to be used.
Experimental example 3

Production of optical recording media (2)
An optical recording medium was produced in the same manner as in Experimental Example 2 except that the glass substrate used in Experimental Example 2 was used instead of a polycarbonate substrate (thickness: 1.0 mm).

Performance Evaluation of Optical Recording Medium To the optical recording medium produced in Experimental Example 2, 880 nm laser pulse light (pulse width: 100 fs, repetition frequency: 80 MHz) was applied to N.P. A. The recording medium was irradiated by squeezing with a 0.55 lens. The presence or absence of deformation of the coating film at the light irradiated portion was confirmed by AFM.
The optical recording medium produced in Experimental Example 3 was irradiated with laser pulse light under the same conditions, and then the coating film was washed with methanol and dried, and the presence or absence of deformation of the polycarbonate substrate was confirmed by AFM.
Table 2 shows the results of confirming by AFM whether or not the coating film or the polycarbonate substrate was deformed at the light irradiated portion in each of the optical recording media subjected to the writing experiment by the above method.
[Comparative Example 1]
Only the polycarbonate substrate not coated with the two-photon absorption compound was irradiated with laser light by the method of Experimental Example 3, and the presence or absence of deformation at the light irradiated portion was confirmed by AFM. The results are shown in Table 2.

  From the above table, the experimental examples 2 and 3 according to the present invention were deformed, whereas the comparative example was not deformed.

Claims (6)

A recording method for an optical information recording medium having a recording component containing at least one non-resonant multiphoton absorption compound, wherein light having a wavelength in which no linear absorption of the recording component exists in a wavelength region from ultraviolet to near infrared. An optical information recording method comprising: recording information by irradiating and causing non-resonant multiphoton absorption, and deforming at least a part of a recording component of the irradiated portion.   2. The deformation is induced by irradiating light having a wavelength longer than an absorption band existing on the longest wavelength side of the non-resonant multiphoton absorption compound and having no linear absorption of the compound. 2. The optical information recording method according to 1.   An optical information recording medium for recording information using the optical information recording method according to claim 1. ^4. The optical information recording medium according to claim 3, wherein the non-resonant multiphoton absorption compound has a two-photon absorption cross-section of 500 GM (1 GM = 10 ⁻⁵⁰ cm ⁴ s photon ⁻¹ ) or more.   5. The optical information recording medium according to claim 3, wherein the multiphoton absorption compound is a transition metal complex compound.   6. The optical information recording medium according to claim 3, wherein information is recorded in three dimensions.