WO2007136051A1

WO2007136051A1 - Optical recording material, optical recording medium using the optical recording material, and method for reproducing optical recording medium

Info

Publication number: WO2007136051A1
Application number: PCT/JP2007/060409
Authority: WO
Inventors: Tetsuo Ozawa; Satoru Imamura; Motoyuki Shigeiwa
Original assignee: Mitsubishi Chemical Corporation
Priority date: 2006-05-22
Filing date: 2007-05-22
Publication date: 2007-11-29

Abstract

This invention provides an optical recording material, which can solve a problem of recording density in an optical recording medium, and an optical recording medium using the optical recording material. The optical recording material comprises a compound having a structure represented by general formula (I). The optical recording medium comprises a recording layer containing the optical recording material. There is also provided a method for reproducing a record in an optical recording medium wherein recording is carried out by photodissociating a compound constituting the optical recording material and comprising a luminescent group and a photodissociating protective group while reproduction is carried out by reading a difference in luminescence intensity between before the photodissociation and after the photodissociation. A - (X - B)n (I) wherein A represents a fluorescence emitting group upon the dissociation of B; X represents a divalent binding group; B represents a photodissociative protective group; and n is an integer of 1 to 6.

Description

Specification

Optical recording material, optical recording medium using the same, and reproducing method of optical recording medium

Field of Invention

The present invention relates to an optical recording material made of a compound having a structure in which a fluorescent group and a photolabile protecting group are bonded, and an optical recording medium containing the optical recording material in a recording layer. Specifically, a photolabile protecting group is bonded to a specific light-emitting group, and the optical recording material has a compound power that changes the light emission intensity by light irradiation, and the optical recording material contains the optical recording material in the recording layer. The present invention relates to an optical recording medium.

The present invention also relates to a method for recording / reproducing the optical recording medium and a novel compound constituting the optical recording material.

Background of the Invention

[0002] Optical recording using laser light has been developed in recent years because it can store and reproduce high-density information recording. An example of the optical recording medium is an optical disk. In general, an optical disc performs high-density information recording by irradiating a thin recording layer provided on a circular substrate with a focused laser beam. The recording is performed by causing thermal deformation such as decomposition, evaporation, and dissolution in the recording layer at the location due to absorption of the irradiated laser beam energy. Also, information is reproduced by reading the difference in reflectance between the part that is deformed by the laser beam and the part that is deformed. However, this method has a limit in recording density.

[0003] In order to solve such problems, there has been extensive research on optical recording materials and recording media using emission intensity changes so far (for example, Patent Documents 1 and 2 and non-patent documents). (Ref. 1, 2).

[0004] Further, for the purpose of further improving the recording capacity, recording is performed with extremely high spatial resolution in an arbitrary place in a three-dimensional space in a recording medium by using multiphoton absorption for recording and reproducing information. Many attempts on “three-dimensional optical memory” have been published (for example, Non-Patent Document 3). Among them, the combination of the above-mentioned change in emission intensity and multiphoton absorption However, the recorded information is not stably stored at room temperature; the emission intensity variation is small, the signal SZN ratio is insufficient; and the components are complicated; (For example, Patent Document 3 11)

On the other hand, in the biotechnology field, two-photon absorption, which has long been one of the multiphoton absorption phenomena, has been used to bond a photo-sensitive protective group (hereinafter referred to as a photolabile protective group) to a physiologically active substance. In addition, active research has been conducted to generate physiologically active substances by irradiating light to substances that have lost their functions, so-called “cage doi compounds” (for example, Non-patent Documents 47). . Non-Patent Document 8 describes a compound in which a photolabile protecting group is bound to a fluorescent dye matrix.

Patent Document 1: Special Table 2001—507137

Patent Document 2: JP-A-2005-8781

Patent Document 3: U.S. Pat.No. 5,268,862

Patent Document 4: Special Table 2003 -529180

Patent Document 5: Special Table 2005— 517769

Patent Document 6: Special Table 2005-520272

Patent Document 7: Japanese Patent Laid-Open No. 2003-27040

Patent Document 8: Japanese Patent Laid-Open No. 2003-29376

Patent Document 9: Japanese Patent Application Laid-Open No. 2004-352770

Patent Document 10: JP-A-2005-29726

Patent Document 11: JP 2005-100606

Non-patent literature l: Science Vol. 245 p843 (1989)

Non-Patent Document 2: Opt. Commun. Vol. 212 p45 (2002)

Non-Patent Document 3: Opt. Lett. Vol. 16 pl780 (1991)

Non-patent literature 4: Proc. Nat. Act. Sci. USA, Vol. 91 p6629 (1994) Non-patent literature 5: Neu Vol. 18 p351 (1997)

Non-Patent Document 6: Neuron Vol. 19 p465 (1997)

Non-patent document 7: Proc. Nat. Act. Sci. USA, Vol. 96 pll932 (1999) Non-patent document 8: J. Am. Chem. Soc. Vol. 128 p3831 (2006) [0006] The inventions described in Non-Patent Documents 4 to 8 relate to a technique for activating a bioactive substance inactivated by a photolabile protecting group by photodissociation, and the hydrophilicity in the vicinity of PH7 as in the living body. The function was confirmed in a neutral buffer solution. None of the compounds described in Non-Patent Documents 4 to 7 have luminescent properties. In addition, the compound described in Non-Patent Document 8 has a fluorescent dye matrix bonded to a physiologically active substance for the purpose of imparting two-photon absorption, but is not intended to impart luminescence characteristics. Therefore, examples of applying these compounds to the above-mentioned optical recording materials and three-dimensional optical memories, which are excellent in solubility in organic solvents and are required to be contained in the recording layer in a solid state, have so far been strong. .

Summary of the Invention

The present invention has been made paying attention to the problem of recording density in an optical recording medium, an optical recording material capable of providing a solution to the problem of recording density in an optical recording medium, and an optical system using the same. An object is to provide a recording medium.

The optical recording material of the present invention is characterized by having a compound power having a structure in which at least one luminescent group and one photolabile protecting group are bonded.

The optical recording medium of the present invention contains this optical recording material in the recording layer. The optical recording medium recording / reproducing method of the present invention is a recording reproducing method of the optical recording medium, and photodissociates a compound having a luminescent group and a photolabile protecting group constituting the optical recording material. It is characterized in that recording is performed and reproduction is performed by reading a change in emission intensity before and after photodissociation.

Brief Description of Drawings

FIG. 1 is a chart showing fluorescence emission spectra before and after recording on the optical recording medium produced in Example 2 with ultraviolet light.

FIG. 2 is a graph showing the relationship between the weight% of the specific example compound with respect to the acrylic resin of the optical recording medium produced in Example 2, and the fluorescence peak intensity and the fluorescence intensity change rate (contrast) before and after the ultraviolet irradiation for 20 seconds. It is.

FIG. 3 is a chart showing fluorescence emission spectra before and after recording on the optical recording medium produced in Example 3 with ultraviolet light.

FIG. 4 shows fluorescence emission spectra before and after recording with ultraviolet light on the optical recording medium produced in Example 4. It is a chart which shows a torr.

[FIG. 5] In Example 2, when an optical recording medium prepared using acrylic resin “Obtretz OZ1100” is irradiated with ultraviolet rays for 20 seconds and then stored under high temperature and high humidity of 80 ° C. and 85% RH It is a chart which shows the peak intensity change.

Detailed description

[0009] As a result of various studies for improving the recording density, the present inventor has come up with the idea of applying a compound whose emission intensity is changed by light irradiation to optical recording, and has reached the present invention. That is, the gist of the present invention is as follows.

[0010] [1] An optical recording material comprising a compound having a structure in which at least one luminescent group and one photolabile protecting group are bonded.

[2] The optical recording material according to [1], wherein the compound has a compound force having a structure represented by the following general formula (I).

[Chemical 8]

A—— CX-B) n (I)

[In the formula (I), A represents a luminescent group, X represents a divalent linking group, B represents a photolabile protecting group, and n represents an integer of 1 to 6. ]

[3] The optical recording material according to [1] or [2], wherein the luminescent group has multiphoton absorption.

[4] The optical recording material according to any one of [1] to [3], wherein the luminescent group is a fluorescent group.

[0014] [5] The optical recording material according to any one of [1] to [4], wherein the emission intensity increases after light irradiation.

[0015] [6] The compound having the structure represented by the general formula (I) is a compound represented by the following general formula (II): [2], [5] The optical recording material according to any one of the above.

[Chemical 9]

[Formula (n 冲,

R ¹ and R ² each independently have a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an aromatic ring group,

X represents a divalent linking group,

B represents a photolabile protecting group,

a represents an integer of 1 to 3.

Z is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, or — (Ar ¹ ) — (X—B) (where Ar ¹ has a substituent, X represents a divalent linking group, B represents a photolabile protecting group, r and s are each independently 0 or 1, and R ¹ and Ar ¹ are bonded to each other. Which may form a 6-membered ring). ]

[7] The compound having a structure represented by the general formula (I) is a compound represented by the following general formula (III) [2], [5] material.

[Chemical 10]

[Formula (m 冲,

R ³ and R ⁴ each independently have a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an aromatic ring group,

X represents a divalent linking group, B represents a photolabile protecting group,

t is an integer from 0 to 4, and u is an integer from 0 to 6. ]

[8] The optical recording according to any one of [2] and [5], wherein the compound having a structure represented by the general formula (I) is a compound represented by the following general formula (IV): Materials.

[Chemical 11]

[In the formula (IV),

Y represents O— or S—

Ar ² and Ar ³ each independently have a substituent! /, May! / Represent an aromatic ring group,

X represents a divalent linking group,

B represents a photolabile protecting group,

V and w are each independently an integer of 0 to 4. ]

[9] The photolabile protecting group B is selected from the group having the basic force represented by the following general formulas (V), (VI), (VII) and (VIII). None [8] The optical recording material described in any of the above.

[Chemical 12]

[The aromatic rings of the formulas (V) to (VII) may further have a substituent! /.

In the formula (VIII), the represents a R ^9, R ^10, R ¹¹ are each independently optional substituents, at least one of R ^9, R ^10, R ¹ ¹ is substituted, also good , An alkyl group. ]

[10] An optical recording medium comprising the recording layer containing the optical recording material according to any one of [1] to [9].

[11] Recording is performed by photodissociating a compound having a luminescent group and a photolabile protecting group constituting the optical recording material, and reproduction is performed by reading a change in luminescence intensity before and after photodissociation. [10] The method for recording / reproducing an optical recording medium according to [10].

[0021] [12] A compound represented by the following general formula (II):

[Chemical 13]

[Formula (n 冲,

X represents a divalent linking group,

B represents a group represented by the following general formula (V), (VI), (VII), or (VIII),

a represents an integer of 1 to 3.

Z is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, or — (Ar ¹ ) — (X—B) (where Ar ¹ has a substituent, X represents a divalent linking group, B represents a group represented by the following general formula (V), (VI), (VII), or (VIII), and r and s each independently represents 0 or 1, and R ¹ and Ar ¹ may combine to form a 6-membered ring.

[Chemical 14]

R ⁹

— COO-R ¹ . … ―… _-M

R ¹¹

(The aromatic ring of the formulas (V) to (VII) may further have a substituent! /.

In the formula (VIII), the represents a R ^9, R ^10, R ¹¹ are each independently optional substituents, at least one of R ^9, R ^10, R ¹ ¹ is substituted, also good , An alkyl group. ))

According to the present invention, information is recorded with light having a wavelength that can be absorbed by the recording material before recording, and the recorded information is emitted by irradiating with light having a wavelength that can be absorbed by the recording material after recording. Therefore, an optical recording material that can be read by detecting the difference in emission intensity between the recorded portion and the unrecorded portion at that time, and that can solve the problem of recording density in the optical recording medium, and using the same. An optical recording medium can be provided. In addition, since the non-destructive reading with high density is possible, the optical recording material of the present invention is an irreversible material, and therefore has good recording storage stability and is practical. In addition, when the optical recording material of the present invention absorbs multiphotons, nondestructive recording can be performed at an arbitrary position in a three-dimensional space with extremely high spatial resolution, and the recorded information can be read with different emission intensities. Therefore, it is considered that the ultimate high density recording is possible. [0023] Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.

In the present invention, the aromatic ring means a ring having aromaticity, that is, a ring having a (4m + 2) π electron system (m is a natural number). The skeleton structure is usually a 5- or 6-membered monocyclic ring or an aromatic ring composed of 2 to 6 condensed rings, including an aromatic hydrocarbon ring, an aromatic heterocycle, an anthracene ring. In addition, condensed rings such as a force rubazole ring and an azulene ring are also included. “…., A ring group” such as “aromatic ring group” is a monovalent substituent obtained by taking one hydrogen atom of such a ring.

In the present invention, “may have a substituent” means that it may have one or more substituents.

[0025] The optical recording material of the present invention is a compound having a structure in which at least one luminescent group and one photolabile protecting group are bonded.

The compound having a structure in which at least one luminescent group and one photolabile protecting group constituting the optical recording material of the present invention are bonded is a fluorescent luminescent material having at least one multiphoton absorption property. A compound having a structure in which a group and one photolabile protecting group are bonded is particularly preferred. A compound having a structure represented by the following general formula (I) (hereinafter sometimes referred to as “compound (I)”) .).

[0026] [Chemical 15]

A—— (X-B) n (I)

[0027] [Compound (1)]

The compound (I) suitable for the present invention is described below.

In the general formula (I), A representing a luminescent group has a property of emitting photons having energy different from the absorbed photons by simultaneously absorbing one or more photons. It is not particularly limited as long as it is a thing, but specifically, for example, a coumarin type And a group having a skeleton, a fluorescein skeleton, or a benzoxaziazole or benzothiadiazole skeleton.

This luminescent group A is preferably a fluorescent group having multiphoton absorption.

[0028] <Divalent linking group X>

X representing a divalent linking group is not particularly limited as long as it has a property that two covalent bonds can be formed through X. Specifically, for example, OS or NR— Etc. O or NR is preferred in terms of ease of synthesis. Here, R may be a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a substituent, an alkoxy group, or a substituent. Represents an aromatic ring group. Specific examples include those described later as in general formula (II).

[0029] <Photolabile protecting group B>

B, which represents a photolabile protecting group, is not particularly limited as long as it has a property of being dissociated by light absorption. For example, Chem. Soc., Perkin Trans 1, 1 page 25, 2002 Synthesis, 1 page, 1980; Org. Photochem., 9 卷, 225 pages, 1987; Trends Biotechnol., 18 卷, 64 pages, 2000, etc. Specifically, for example, 2-trobenzyl group, coumarylmethyl group, 4-hydroxyphenacyl group, carboxylic acid ester group, and the like can be mentioned.

[0030] The number η of the photolabile protecting groups 結合 bonded to one luminescent group は is not particularly limited as long as it is 1 or more. However, it is usually from the standpoint of availability of raw materials and organic synthesis. 1 6 is preferable, and 1 4 is preferable.

Here, light emission obtained by exciting the optical recording material of the present invention by light irradiation or the like mainly includes fluorescence and phosphorescence, but is not limited to these unless it exceeds the gist. There is no.

[0032] The compound represented by the general formula (I) includes a wavelength having high measurement sensitivity in a silicon photodetector in which the emission intensity of the luminescent group is large and the emission wavelength is usually used, that is, usually. 300-: L 100 nm, particularly preferably 400 Since it is desirable to have an emission wavelength at 1000 nm, specifically, a compound in which A representing a luminescent group is a group having the coumarin skeleton is represented by the following general formula (II ) (Hereinafter sometimes referred to as “compound (11)”). ) Represents a luminescent group A is a compound represented by the following general formula (III) (hereinafter sometimes referred to as “compound (111)”) as a compound in which A is a group having the fluorescein skeleton. As a compound in which A representing a functional group is a group having the benzoxaziazole or benzothiadiazole skeleton, it may be referred to as a compound represented by the following general formula (IV) (hereinafter referred to as “compound (IV)”). Are particularly preferred.

[0033] [Chemical 16]

[0034] [In the formula (II),

X represents a divalent linking group,

表し represents a photolabile protecting group,

a represents an integer of 1 to 3.

[0035] [Chemical 17]

[0036] [In the formula (III), R ³ and R ⁴ each independently have a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an aromatic ring group,

X represents a divalent linking group,

B represents a photolabile protecting group,

t is an integer from 0 to 4, and u is an integer from 0 to 6. ]

[0037] [Chemical 18]

[0038] [In the formula (IV),

Y represents O— or S—

Ar ² and Ar ³ each independently have a substituent! /, May! / Represent an aromatic ring group, X represents a divalent linking group,

B represents a photolabile protecting group,

V and w are each independently an integer of 0 to 4. ]

[0039] {About Compound (II)}

Here, means that one NR as X described in the general formula (I) has. Specific examples of the halogen atom at R °, R ¹ , and R ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and the alkyl group has 1 to 8 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, iso propyl group, butyl group, iso butyl group, sec butyl group, tert butyl group, hexyl group, octyl group and the like. The alkoxy group preferably has 1 to 8 carbon atoms. Specifically, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, iso butoxy group, sec butoxy group, tert Butoxy group, hexyloxy group, octyloxy group and the like. Specific examples of the aromatic ring group include a benzene ring, a naphthalene ring, an anthra group. Examples include groups derived from sen ring, furan ring, thiophene ring, pyridine ring, quinoline ring, benzofuran ring, benzothiophene ring and the like.

[0040] The alkyl group, alkoxy group, and aromatic ring group of R ¹ , R ¹ , and R ² may further have a substituent. The substituent that R °, R ¹ and R ² may further have may be any substituent as long as it satisfies the function of the present invention. Specifically, the following [ Examples include the groups exemplified in Substituent Group W].

[0041] [Substituent group W]

Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom)

Nitro group

Hydroxy group

Cyan group

Carboxyl group

Sulfo group

Alkyl group which may have a substituent (methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso butyl group, sec butyl group, tert butyl group, hexyl group, octyl group, tetradecahydro Carbon number such as anthral group is usually 1-20, preferably 1-10, linear or branched, cyclopropyl group, cyclohexyl group, cyclohexyl group etc. -20, preferably 5-10 cycloalkyl groups)

Alkyl group which may have a substituent (Buyl group, propenyl group, butur group, 2-methyl-1 probe group, hexyl group, otatur group, etc. 20, preferably 2 to 10 linear or branched ones)

The alkyl group which may have a substituent (e.g., an ethur group, a propylene group, a butur group, a 2-methyl-1-propyl group, a hexynyl group, an octynyl group, etc. usually has 2 to 20, preferably 2 to 10 linear or branched)

An aryl group which may have a substituent (an aryl group having 6 to 18, preferably 6 to 10 carbon atoms, such as a phenol group, an anthral group, a phenanthryl group, or a phenyl senyl group) ) Heterocyclic group (5- to 6-membered monocycle or 2- to 6-fused ring heteroaryl group, 5- to 6-membered mono-cyclic ring or 2 to 6-fused ring) Hetero atoms include nitrogen atoms, oxygen atoms, sulfur atoms, etc. Specific examples include 5-membered rings such as chenyl groups, pyridyl groups, 2-piberidyl groups. Group, 6-membered ring such as 2-piperazinyl group, 5- or 6-membered 2-6 condensed ring such as benzocenyl group, carbazolyl group, quinolinyl group, octahydroquinolinyl group)

Alkoxy group which may have a substituent (methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, etc. In which the number of carbon atoms is usually 1 to 9, preferably 2 to 8)

It may have a substituent, and a (hetero) aryloxy group (phenoxy group, naphthyloxy group and the like usually having 6 to 18, preferably 6 to 10 carbon atoms, such as a 2-hydroxy group, Heteroaryl containing 2-furyloxy group, 2-quinolyloxy group or the like, usually having 5 to 18, preferably 5 to 10 carbon atoms, and a hetero atom selected from nitrogen atom, oxygen atom, sulfur atom, etc. An oxy group, etc.)

Alkylthio group which may have a substituent (methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, hexylthio group, octylthio group Group having 1 to 9 carbon atoms, preferably 2 to 8 carbon atoms)

May have a substituent! / May be an arylthio group (a phenylthio group such as a phenolthio group or a naphthylthio group, usually having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, Heteroarylthio groups including those in which the number of carbon atoms of the group, 2-furylthio group, 2-quinolylthio group and the like is usually 5 to 18, preferably 5 to 10, and a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is selected. Etc.)

It may have a substituent, and may be an alkoxy carbonyl group (methoxy carbonyl group, ethoxy carbonyl ole nole group, propoxy ano rep eno ole group, isoprop oxy ano bon nole group, tert-butoxy carbo ol group, acetyloxy Group, benzoyloxy group and the like having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms) It may have a substituent, and a (hetero) aryloxycarbonyl group (phenoxycarbo)

Such as aryl group, naphthyloxycarbonyl group and the like having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, such as 2-hydroxycarbonyl group, 2-furyloxycarbonyl group. , A 2-quinolyloxycarbonyl group or the like having a carbon number of usually 5 to 18, preferably 5 to 10, and a heteroaryl containing a heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom, etc. An oxycarbonyl group, etc.)

An amino group which may have a substituent (e.g., an ethyl group, a dimethylamino group, a methylethylamino group, a dibutylamino group, a piperidyl group, etc. having 2 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Alylamino group having 6-30, preferably 6-15 carbon atoms such as ruamino group, dinaphthylamino group, naphthylphenylamino group, ditolylamino group, di (2-chenyl) amino group, di (2-furyl) amino group, etc. Having 5 to 30 carbon atoms, preferably 6 to 15 carbon atoms, including hetero atoms such as nitrogen atoms, oxygen atoms and sulfur atoms, heteroaryl amino groups, and phenyl (2-cell) amino Group having 11 to 30 carbon atoms, preferably 12 to 16 carbon atoms such as heteroarylamino group)

An acyl group which may have a substituent (including an acyl group having 1 to 30, preferably 1 to 20 carbon atoms such as an acetyl group, a benzoyl group, a formyl group, and a bivaloyl group) Or a siloxy group (acetoxy group, benzoyloxy group and the like having 1 to 30 carbon atoms, preferably 1 to 20 acyloxy groups)

It may be substituted. Acylamamino group (for example, an acylamino group having 1 to 30, preferably 1 to 20 carbon atoms, such as an acetylamino group or a benzoylamino group)

An ureido group which may have a substituent (a ureido group having 1 to 30, preferably 1 to 20 carbon atoms, such as a methylureido group, a ureido group or a ferureido group)

It may have a substituent. Sulfonamide group (including sulfonamide groups such as methanesulfonamide group and benzenesulfonamide group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms) Or a rubamoyl group (for example, a rubamoyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as a rubamoyl group, a methylcarbamoyl group, and a jetylcarbamoyl group)

It may have a substituent, and it may be a sulfamoyl group (sulfamoyl group, methylsulfamoyl group). A rubamoyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a sulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group)

It may have a substituent group. Sulfamoylamino group (sulfamoylamino group, ethyl sulfamoylamino group, dimethylsulfamoylamino group, tolsulfamoylamino group, etc.) May have 1 to 30 and preferably 1 to 20 rubamoylamino groups. It may have a substituent, and may be a sulfol group (a methanesulfol group, a phenolsulfol group or the like having 1 carbon number). -30, preferably 1-20 sulfol groups)

It may have a substituent and may be a sulfier group (e.g., a sulfiel group having 1 to 30, preferably 1 to 20 carbon atoms, such as an ethane sulfiel group or a phenol sulfyl group) [0042] R ° is generally a hydrogen atom, but the above alkyl group is preferred from the viewpoint of solubility and heat-and-moisture resistance.

[0043] Also, R ¹ is preferably a hydrogen atom, an alkyl group, or a halogen atom! /.

[0044] Further, as R ² , a hydrogen atom, an alkyl group, or a halogen atom is preferable.

[0045] <Z>

Z halogen atom, and as the alkyl group, R °, R ^1, like the levator Gerare as in R ² also,, Z Gar (Ar ^¹⁾ - Ar ¹ when it is (X-B) Specific examples of the aromatic ring group include groups derived from a benzene ring, naphthalene ring, anthracene ring, furan ring, thiophene ring, pyridine ring, quinoline ring, benzofuran ring, benzothiophene ring, and the like. Are, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, hydroxy group, carboxy group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec 1 to 8 carbon atoms such as butyl, tert butyl, hexyl, octyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec Examples thereof include an alkoxy group having 1 to 8 carbon atoms such as a xy group, a tert butoxy group, a hexyloxy group and an octyloxy group.

[0046] The photolabile protecting group B will be described later.

[0047] a is preferably 1 to 3, and more preferably 1. When a is 2 or more, the 2 or more X—B groups may be the same or different. From the viewpoint of easy organic synthesis and the availability of raw materials, when a is 1, the substitution position of —X—B is preferably 6th or 7th, and a is 2 or more. In some cases, it is preferable that at least the 6-position and the 7-position have one X—B substituted.

[0048] Specific examples of the 6-membered ring which may be formed by combining R ¹ and Ar ¹ include a benzene ring and a pyrone ring.

[0049] In particular, Z is a benzene ring as Ar ¹ , 1 O as X, or 1 NR— (wherein R is as described above). Preferred is one having a photolabile protecting group B represented by

[0050] {About Compound (III)}

Examples of the halogen atom, alkyl group, alkoxy group, aromatic ring group and the substituent that they may have in R ³ and R ⁴ are the same as those in R ¹ , R ¹ , and R ² in the general formula (II). And X is the same as in general formula (II). The photolabile protecting group B will be described later. In the formula (III), when two B—X groups and t and u are 2 or more, two or more R ³ and R ⁴ may be the same or different. .

[0051] From the viewpoint of ease of synthesis and solubility in a coating solvent, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group or a halogen atom, and X is preferably —NR— (R As described above, t and u are preferably independently 0-2.

[0052] {About Compound (IV)}

Examples of the aromatic ring group of Ar ² and Ar ³ and the substituent thereof are the same as those in Ar ¹ of the general formula (Π) (however, a divalent group). X can also be the same as in general formula (II). The photolabile protecting group B will be described later. In the formula (IV), two B—X groups may be the same or different from each other.

[0053] Ar ² and Ar ³ are each independently a divalent group derived from a phenylene group, a naphthylene group, an anthracylene group, a phenanthrylene group, a pyrenylene group, and thiophene, pyridine, furan, galbazole, or quinoline ring. Preferred as X is —NR (as described above) is preferred. V + w is preferably 2-6.

[0054] {Regarding Photolabile Protecting Group B in Compounds (11), (111), and (IV)}

As the photolabile protecting group B, the aforementioned 2-trobenzyl group may be represented by the following general formula (V) (hereinafter referred to as “ 2— -Trobenzyl group (V) ”. In addition, the group represented by the following general formula (VI) (hereinafter sometimes referred to as “coumarylmethyl group (VI)”) as the coumarylmethyl group is also the 4-hydroxyfunacyl group. A group represented by the following general formula (VII) (hereinafter sometimes referred to as “4-hydroxyphenacyl group (VII)”), and the carboxylic acid ester group represented by the following general formula (VIII): Are particularly preferred respectively (hereinafter sometimes referred to as “carboxylic acid ester group (VIII)”).

[0055] [Chemical 19]

[0056] [The aromatic rings of the formulas (V) to (VII) may further have a substituent! /.

In the formula (VIII), R ⁹ , R ¹⁰ and R ¹¹ each independently represents an arbitrary substituent, but at least one of R ⁹ , R ¹⁰ and R ^] ¹ may have a substituent. , An alkyl group. ]

[0057] The aromatic rings of formulas (V) to (VII) may further have a substituent and specific examples of R ^{9 to} R "of formula (VIII) include the above-mentioned [Substituent group W ] Are exemplified.

[0058] The aromatic rings of formulas (V) to (VII) may further have substituents and When the group of R ¹¹ further has a substituent, examples of the substituent include those exemplified in the above-mentioned [Substituent group W].

[0059] <Preferred examples of bistrobenzyl group (V)>

When the 2-trobenzyl group (V) has a substituent, or preferably has an alkyl group or an alkoxy group as a substituent, the number of substituents is 1 or 2 The preferred substitution positions are 4 and 5 positions. When there are two or more substituents, the two or more substituents may be the same or different.

[0060] Specific examples of the 2-trobenzyl group (V) include 2-trobenzyl group, 2-tro 6 fluorofluoro group, 2-tro-4-chlorobenzil group, 2-tro-5-chlorobenzyl group, 2 -Tro 6 chloro benzyl group, 2 -tro 4 bromo benzyl group, 2, 4 di-tro benzyl group, 2 -tro 5 hydroxy benzyl group, 2 -tro 4 4-force ruoxy benzyl group, 2- Toro 3 methylbenzyl group, 2 -tro 4 methylbenzil group, 2-tro 6-methylbenzyl group, 2-toro-4,5 dimethoxybenzyl group, 2-toro 3, 4, 5 trimethoxybenzyl group, 2-toro — 4 Dodecyloxy— 5— Methoxybenzyl group, 2-tro— 4 Ethoxycarbol penzyl group, 2 — Toro — 4— tert Butoxycarbol penzyl group, 2-tro 4-Methylaminocarbol penzyl group, 2 — Toro 4-phenol penzyl group 2-tro-5 benzyloxybenzyl group and the like.

[0061] <Preferred example of coumarylmethyl group (VI)>

Coumarylmethyl group (VI) has no substituent, or preferably has a halogen atom, a hydroxy group, an alkyl group, or an alkoxy group, and the number of substituents is preferably 1 or 2. As the substitution positions, the 6th and 7th positions are preferred. When there are two or more substituents, the two or more substituents may be the same or different.

[0062] Specific examples of the coumarylmethyl group (VI) include 7-hydroxycoumarin-4-ylmethyl group, 7-methoxycoumarin-4-ylmethyl group, 7-methoxymethoxycoumarin-4-ylmethyl group, 7-hydroxycarbo 4-Luylmethoxycoumarin 4-ylmethyl group, 7- n-Proxoxycarboromethoxycoumarin 4-ylmethyl group, 7- tert Butoxycarbolume Toxicoumarin-4-ylmethyl group, 7-Dimethylaminocoumarin 4-ylmethyl group, 7- Jetylaminocoumarin-4-ylmethyl group, 7-ethoxycarbo-laminocoumarin-4-ylmethyl group, 7- tert-butoxycarbo-methylmethylaminotamarin 4-ylmethyl group, 6-bromo-7-hydroxycoumarin- 4-ylmethyl Groups, 6-bromo-7-acetyloxycoumarin 4-ylmethyl group, 6-ethyl 7-hydroxycoumarin 4-ylmethyl group, 6,7-dimethoxycoumarin-4-ylmethyl group, and the like.

[0063] <4 Preferred example of hydroxyphenacyl group (VII)>

4-Hydroxyphenacyl group (VII) has a substituent! /, N! /, Or a substituent preferably having an alkyl group or an alkoxy group as a substituent. The number is preferably 1 or 2. When there are two or more substituents, the two or more substituents may be the same or different.

[0064] Specific examples of 4-hydroxyphenacyl group (VII) include 4-hydroxyphenacyl group, 2,4-dihydroxyphenacinole group, 2,3,4 trihydroxyphenacinole group, 2 , 4, 6 Trihydroxyphenacyl group, 2,4 dihydroxy-3 methylphenacyl group, 2,4 dihydroxy-5 methylphenacyl group, 2,4 dihydroxy-5 ethenylphenacyl group, 2,4-dihydroxy-1-5-n-hexylphenacyl group, Examples include 3,4-dihydroxy-1,5-ditrophenacyl group, 3,5-dimethyl-4-hydroxyphenacyl group, 3-methoxy-4-hydroxyphenacyl group, 3,5-dimethoxy-4-hydroxyphenacyl group, and the like.

The alkyl group represented by R ⁹ , R ¹⁰ and R ^{11 in} the general formula (VIII) preferably has 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. Group, n-butyl group, isobutyl group, sec butyl group, tert butyl group, hexyl group, octyl group and the like.

[0066] Specific examples of the carboxylic acid ester group (VIII) include iso-propoxycarbol group, tert-butoxycarbol group, tert-amyloxycarbol group and the like.

[0067] {Photoacid generator)

When the photolabile protecting group B of the compounds (I) to (IV) in the present invention is a carboxylic acid ester group (VIII), the optical recording material of the present invention has a photoacid generator that generates an acid by light irradiation. It is preferable to use an agent in combination. Photoacid generators in this case include BF-, SbF-, PF-, CIO- and other salts such as diazo-um salts, phospho-um salts, sulfo-um salts, and jordonium salts, and diazomethane derivatives. But

4 6 6 4

Can be mentioned. Preferred photoacid generators include diphenylsulfonyl trifluoromethane sulfonate, diphenyl rhodium hexafluorophosphate, triphenylsulfo-trifluoromethane sulfonate, triphenylsulfotetrafluoroborate, Examples thereof include bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like.

These may be used alone or in combination of two or more.

[0068] {Molecular weight of compounds (I), (II), (III), (IV)}

The molecular weight of the compound (1), preferably the compounds (II), (III), (IV) is usually 10,000 from the viewpoints of ease of synthesis, stability of the compound, solubility in a solvent, compatibility with a polymer, etc. Or less, preferably 6000 or less.

The compound (1), preferably the compounds (II), (III), (IV), is usually preferably insoluble in water for the purpose of improving the storage stability of the recording medium. Here, “water insoluble” means that the solubility power in water at 25 ° C. and 1 atm is usually 0.1% by weight or less, preferably 0.01% by weight or less.

In addition, the compound (1), preferably the compounds (II), (III), (IV), can be easily handled in the process of producing a recording medium, and the recording / reproducing characteristics can be improved by controlling the concentration. Which reason force It is preferable that the solubility with respect to a coating solvent is high. Here, the high solubility in the coating solvent means that the solubility in the coating solvent at room temperature is usually 0.1% by weight or more, preferably 0.1% by weight or more.

[0069] {Specific examples of compounds (II), (III), (IV))

Specific examples of the compounds (11), (111), and (IV) are shown below, but the present invention is not limited to the following specific examples as long as the gist thereof is not exceeded.

[0070] [Chemical 20]

[0071] [Chemical 21]

twenty two] Compound (m)>

twenty three] Compound (III)>

[0074] [Chemical 24]

Compound αν)>

W-8

[0075] [Chemical 25]

IV-26 [0076] In the above specific examples, "B", "B", "B", and "B"

1 2 3 4

The photolabile protecting group shown.

[0077] [Chemical 26]

B ₃ ; rt)

[0078] {Synthesis Method of Compounds (II), (III), (IV)}

Examples of the reaction for linking the luminescent group A and the photolabile protecting group B include those described in Greene, Protective Gruops Inorganic Synthesis drd Ed. Wiley, Larock, Comprehensive Organic Transformations 2nd Ed. A known method can be used.

[0079] (a) In the case where the divalent linking group X is —O 2

For example, a hydroxide of a luminescent group A and a halide of a photolabile protecting group B (particularly preferably bromide, chloride, about 1 to 5 equivalents per reaction site), acetone, dioxane, Base in a solvent such as tetrahydrofuran, N, N dimethylformamide (specifically, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium hydride, tert-butoxypotassium, tert-butoxysodium, etc.) Stirring in the presence of a base, lithium di (isopropyl) amide, lithium di (trimethylsilyl) amide, lithium reagents such as n-BuLi, sec-BuLi, and tert-BuLi, and organic bases such as triethylamine) at room temperature to the refractory temperature of the solvent. To do. Although the reaction time varies depending on the substrate, the end point of reaction, which is preferably about 1 to 10 hours, is confirmed by thin layer chromatography, high performance liquid chromatography, etc., and the end point is judged. After completion of the reaction, the reaction solution is cooled to room temperature and poured into ice water. Extract with ethyl acetate, methylene chloride, chloroform, jetyl ether, etc. to obtain crude product. This can be purified by column chromatography to obtain the desired product. The reaction and the purification are more preferably performed while blocking light.

[0080] (b) When the divalent linking group is NR- For example, an amine compound having a luminescent group A (the amine may be mono-substituted or unsubstituted) and a halogenated compound having a photolabile protecting group B (particularly preferably, for one point of bromide, chloride, reaction site) 1 equivalent to 1.5 equivalent) in a solvent such as acetone, dioxane, tetrahydrofuran, N, N-dimethylformamide, etc. (specifically, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide) , Potassium hydroxide, sodium methoxide, sodium hydride, tert-butoxypotassium, tert-butoxysodium and other inorganic bases, lithium di (isopropyl) amide, lithium di (trimethylsilyl) amide, n-BuLi, sec-BuLi In the presence of a lithium reagent such as tert-BuLi, or an organic base such as triethylamine) (addition of a phase transfer catalyst may be preferable) ), Stirred at reflux temperature of about room temperature to the solvent. Although the reaction time varies depending on the substrate, the end point of reaction, which is preferably about 1 to 10 hours, is confirmed by thin layer chromatography, high performance liquid chromatography, etc., and the end point is judged. After completion of the reaction, the reaction solution is cooled to room temperature and poured into ice water. Extract with ethyl acetate, methylene chloride, chloroform, jetyl ether, etc. to obtain crude product. This can be purified by column chromatography to obtain the desired product. The reaction and purification are more preferably performed while blocking light.

[0081] Further, as another method, the amine compound of the luminescent group A and the aldehyde compound of the photolabile protecting group B precursor are made non-catalyzed or an inorganic acid such as an acid (for example, acetic acid, sulfuric acid, nitric acid, hydrochloric acid). P- Organic organic acids such as TsOH and PPTS) In the absence of solvent or solvent, methanol and ethanol are added and heated to make an imine intermediate. The imine intermediate is reduced with an reducing agent (for example, a weak reducing agent such as sodium borohydride) to obtain the target compound. This method is particularly useful for unsubstituted amines. The reduction reaction and the purification are more preferably performed while blocking light.

[0082] {Information recording of compound (I) 'reproduction mechanism)

The compound (I) according to the present invention specifically exemplified by the general formula (11), (111), or (IV) is a material for optical recording, and the luminescent group A is photodissociated before light irradiation. Protected with protecting group B, and no or no light is emitted, but photodissociation protecting group B is dissociated by light irradiation, thereby recording information, while light emitting group is recorded by light irradiation. The recorded information can be reproduced by emitting a strong light from the light-emitting matrix having A and reading the light. Therefore, the optical recording material of the present invention comprising such a compound (I) is suitable for use in a recording layer of an optical recording medium.

Also, depending on the nature of the luminescent group A, even when the photodissociation protecting group B is bonded, light is emitted, and information is recorded by light irradiation. On the other hand, the light-emitting host having the luminescent group A emits fluorescence. In some cases, the recorded information can be reproduced by reading the difference in light emission intensity.

[0083] [Optical recording medium]

The optical recording medium of the present invention contains the optical recording material of the present invention as described above in a recording layer.

In the present invention, in order to use the optical recording material for a recording layer of an optical recording medium, for example, a coating liquid containing the optical recording material is applied on a transparent substrate and dried. Made from Aoi Ko. In addition, a resin pellet containing a predetermined amount of the optical recording material is prepared in advance, a recording layer is prepared by a method such as press or injection molding using the resin pellet, and only the recording layer is used. A function as a substrate may be given together by ensuring mechanical strength.

In this case, the optical recording material is not limited to one type, and two or more types may be used in combination.

That is, the optical recording medium of the present invention contains only one kind of the compound (1), preferably compounds (I), (II), (III), which is the optical recording material of the present invention, in the recording layer. 2 or more types may be used in any combination and ratio.

[0084] The coating liquid or the resin pellet for forming the recording layer according to the present invention is a singlet together with the optical recording material in order to impart stability, light resistance, etc. as the recording layer. Oxygen quenchers, recording sensitivity improvers, etc. may be included.

[0085] Examples of the singlet oxygen quencher include acetyl compounds such as acetyl cettonate, bisphenol dithiol, salicylaldehyde oxime, bisdithio adiketone, and transition metals. Species or two or more are used in combination.

[0086] Examples of the recording sensitivity improver include metal compounds in which a metal such as a transition metal is contained in a compound in the form of atoms, ions, clusters, and the like. Complex, azomethine complex, phenol hydroxyamine complex, phenantorin phosphorus complex, dihydroxyazobenzene complex, dioxime complex, nitrosaminophenol complex, pyridyltriazine complex, acetylyla Examples thereof include organometallic compounds such as a setnerate complex and a metacathene complex, and one or more of these are used in combination.

[0087] Further, the coating liquid preferably contains a binder in order to improve the film-forming property. The binder includes known ones such as acrylic resin, methacrylic resin, polybulal alcohol, polybutylpyrrolidone, ketone resin, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate. Two or more types are used in combination.

[0088] The coating liquid is prepared by dissolving the optical recording material of the present invention, the binder, and, if necessary, the singlet oxygen quencher, the recording sensitivity improver, and the like in a solvent.

[0089] The solvent is not particularly limited as long as it does not damage the transparent substrate described later. For example, ketone alcohol solvents such as diacetone alcohol, 3hydroxyl-3-methyl-2-butanone, methylcetosolve, cellosolve solvents such as Echiruse port cellosolve, hexane _n one, n- chain hydrocarbon solvents such as octane, cyclohexane, methylcyclohexane, hexane Echirushikuro, hexane dimethylcyclopentadienyl, hexane n- Buchirushikuro, t Alicyclic hydrocarbon solvents such as butylcyclohexane and cyclooctane; ether solvents such as diisopropyl ether and dibutyl ether; and perfluorocarbons such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol. Fluoroalkyl alcohol solvent, methyl lactate, ethyl lactate, isobutyrate Examples include hydroxyester solvents such as methyl acid, and one or more of these are used in combination. Among these, tetrafluoropropanol is particularly preferred because it is preferred for perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol. I like it.

[0090] The concentration of the optical recording material of the present invention in the coating solution is usually 0.01% by weight or more, preferably 0.1% by weight or more, based on the total solid content in the coating solution. , Particularly preferably 0.5% or more, usually 50% or less, preferably 5% or less.

Further, as the transparent substrate on which the coating liquid is applied and the recording layer is formed, a transparent substrate with respect to the laser beam to be used, such as glass and various plastics, is preferably used. Plastics include acrylic resin, methallyl resin, polycarbonate resin, salt resin resin, acetate resin resin, nitrocellulose, polyester resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene Examples of the resin include epoxy resin, epoxy resin, and the like, and an injection molded plate in which polycarbonate resin is preferred from the viewpoint of productivity, cost, moisture absorption resistance and the like is more preferable. In addition, when the recording layer is prepared by a method such as press or injection molding using the resin pellets and the mechanical strength is secured only by the recording layer, the function as a substrate is also provided. Materials are preferably used.

[0092] Examples of a method for applying the coating liquid onto the transparent substrate include a doctor blade method, a cast method, a spin coating method, and a dipping method. Among these, mass productivity, cost, etc. From the viewpoint of spin coating, the spin coating method is preferable.

[0093] The thickness of the recording layer formed on the transparent substrate is not particularly limited, but is usually 5ηπ! ˜50 μm, preferably 10 nm to 10 μm, more preferably 50 nm to 5 μm.

[0094] In addition, when a recording layer is prepared by a method such as pressing or injection molding using a resin pellet and mechanical strength is secured only by the recording layer, the function as a substrate is also provided. The thickness of the recording layer is usually 100 μm to 20 mm, preferably 200 μm to 10 mm.

[0095] As an optical recording medium in the present invention, an undercoat layer may be provided on the transparent substrate, and the recording liquid may be formed by applying the coating liquid on the transparent substrate and drying it. Silver is preferable as the metal in such a case where a metal reflective layer and a protective layer made of gold, silver, aluminum, or an alloy thereof are provided on the formed recording layer to serve as a high reflectance medium.

[0096] In this case, the metal reflective layer is formed by vapor deposition, sputtering, ion plating, or the like, and further improves the adhesion between the recording layer and the metal reflective layer, or reflects the reflectance. An intermediate layer may be provided between both layers for the purpose of increasing the thickness. For forming the protective layer, for example, an ultraviolet curable resin is used.

[0097] The optical recording material of the present invention in the recording layer containing the optical recording material of the present invention (that is, compound (1), preferably compounds (I), (,), (III)). The concentration of the coating liquid applied and dried In the case of the recording layer formed by the above, 0.01 to: LOO wt%, particularly 0.1 to 50 wt% is preferable, and in the case of the recording layer with the resin pellet, 0.01 It is preferably -95% by weight, particularly 1-25% by weight. If the concentration of the optical recording material is less than this range, sufficient recording / reproduction characteristics cannot be obtained. If the concentration is too large, sufficient strength can be obtained with a relatively low resin concentration as a binder in the case of a recording layer made of resin pellets. Absent.

[Recording / reproducing method of optical recording medium of the present invention]

The recording / reproducing method of the optical recording medium of the present invention irradiates recording light to photodissociate the optical recording material of the present invention, that is, the compound (1), preferably the compounds (I), (II), (III). This is characterized in that recording is performed and reproduction is performed by reading the change in emission intensity before and after photodissociation.

[0099] The recording light used in the optical recording medium of the present invention may be any wavelength that can excite the dissociation reaction of the photodissociating group, but for high-density recording, the shorter the wavelength, the particularly preferred wavelength 350 A laser beam of ˜530 nm is preferred. Typical examples of such laser light include blue laser light with center wavelengths of 405 nm and 410 nm, blue-green high-power semiconductor laser light with center wavelength of 515 nm, and the like. In addition, using a long-wavelength laser beam having a wavelength of about 500 to 900 nm and performing three-dimensional recording using the two-photon absorption of the optical recording material enables higher-density recording.

[0100] The reproduction light used in the optical recording medium of the present invention may be of a wavelength that can excite the luminescent group, but in order to reproduce information recorded at high density, the shorter the wavelength, Particularly preferred is a laser beam having a wavelength of 350 to 530 nm. As a representative example of such a laser beam, there is a laser beam used for the recording light. In addition, by using a laser beam having a wavelength of about 500 to 90 Onm and performing three-dimensional reproduction using the multiphoton absorption characteristics of the optical recording material, higher density reproduction is possible.

Note that it is preferable to use the same laser light for the recording light and the reproducing light because the system can be simplified.

In addition, in order to avoid deterioration (decomposition) of the optical recording material of the present invention due to reproduction light and deterioration of the unrecorded portion (photodissociation) particularly when the wavelengths of the recording light and the reproduction light are close to each other, The irradiation intensity of the reproduction light used for the optical recording medium is sufficiently smaller than the recording light. It is preferable that the irradiation intensity of the reproduction light is 1/5 or less, preferably 1/50 or less of the irradiation intensity of the recording light.

[0101] The optical recording medium of the present invention provides a sufficient SZN ratio with a small component with a large change in emission intensity obtained by photodissociation of the optical recording material of the present invention by light irradiation. The recorded information is stably stored at room temperature.

Here, the change in emission intensity means light emitted from a recording medium by irradiating the recording medium with light having a wavelength of about 250 to 400 nm using a fluorescence spectrophotometer (for example, “F-4500” manufactured by Hitachi, Ltd.). The spectrum is measured to indicate the rate of change of emission intensity near the emission peak before and after light irradiation, and is usually 5 or more, preferably 10 or more, particularly preferably 20 or more. In addition, stable storage at room temperature means that when left in a high-temperature, high-humidity environment at 80 ° C and 85% RH for 100 hours, the change in light emission intensity of the light-irradiated recording area is usually within 50%, preferably 25% Say that it is within.

Example

[0102] The ability to describe the present invention more specifically with reference to the following examples The present invention is not limited to the following examples unless the gist thereof is exceeded.

[0103] Example 1

Synthesis of Specific Example Compound II 1 below

[Chemical 27]

(Specific compounds Π— 1)

3— (p aminophenol) 1-7 aminocoumarin 0.8 g and potassium carbonate 1.38 g dissolved in 30 ml N-methylpyrrolidone and heated to 110 ° C. with stirring at 110 ° C. ―-Add 28 g of trobenyl dichloride, heat and stir for 5 hours, cool to 25 ° C, drain the reaction solution into 100 ml of water, extract with ethyl acetate, and then add the acetic acid solution with sodium sulfate. Dry, concentrate, and column chromatography on silica (eluent; ethyl acetate Z-toluene = 1 Purification by Z4) yielded 0.29 g of the specific compound II-1 as the target product.

[0105] Visible region absorption (λ max): 384 nm (toluene)

Fluorescence emission peak wavelength (excitation wavelength: 325 nm): 473 nm (toluene)

Mass spectrum DEI (positiveionmode) method: mZz = 522 (M +), 520, 387, 339,

311

Two-photon absorption cross-sections are evaluated by Kato, S .; Matsumoto, T .; Ishi-1, T .; Thiemann, T .; S higeiwa, M .; Gorohmaru, H .; Maeda, S .; Yamashita, Y. A method similar to that described in Supporting Information of Mataka, S. Chem. Commun. 2004, 2342-2343. A femtosecond titanium sapphire laser (wavelength: 800 nm, pulse width: 120 fs, repetition: lkHz, output: 2 mjZ pulse) was used as the measurement light source, and the two-photon absorption cross section was measured by appropriately attenuating the output from the laser. . When changing the laser wavelength, laser light of a predetermined wavelength was obtained using a wavelength converter (TOPAS). The measurement was changed within the range of the excitation light density L～40GWZcm ² using Z- scan method. As a measurement sample, a solution in which the compound was dissolved in DMSO at a concentration of 5 mmol Zl was used, and this solution was put into a four-sided transparent lcm square quartz cell for measurement.

Specific Example Compound II 1 had a two-photon absorption cross section at a wavelength of 800 nm of 2 [GM] and a two-photon absorption cross section at a wavelength of 650 nm of 88 [GM].

[0107] Example 2

Production of optical recording media and changes in fluorescence intensity

Specific examples Compound [pi-1 synthesized in Example 1 and 0. 5 mg weighed, 5 weight ^_0/0 solution of an acrylic榭脂(Mitsubishi Les Yon made "Atari pet VH- 5") (solvent: 3 - hydroxy - 3 Methyl-2-butanone) A coating solution was prepared by dissolving in lg. This coating solution is dropped onto a 0.6 mm thick polycarbonate substrate, left to stand for one day and air-dried, and further dried at a temperature of 100 ° C for 30 minutes to form a 10 μm-thick recording layer. An optical recording medium was prepared.

The fluorescence emission of the obtained optical recording medium was measured with a spectrofluorometer (“F-4500” manufactured by Hitachi, Ltd.), and the fluorescence emission spectrum is shown in FIG. 1 (curve a). Next, a spot type ultraviolet irradiation device (“Spot Cure UIS-50101 AA” manufactured by Usio Electric, After irradiating with UV light for 1 second and 20 seconds using an ultra-high pressure mercury lamp (USH-500BY1 manufactured by Usio Electric, main wavelength: 365 nm, irradiation intensity: 300 mWZcm ² ), excitation wavelength is measured with the spectrofluorometer. Fluorescence emission is measured at 325 nm (Fig. 1 also includes fluorescence emission peaking at an excitation wavelength of 325 nm, a multiple wavelength of 650 nm, and a wavelength of 350 nm from a polycarbonate substrate), and the fluorescence after irradiation for 1 second. Figure 1 shows the emission spectrum as a curve and the fluorescence emission spectrum after 20 seconds of irradiation as curve c. In the curve a, the intensity of fluorescence emission with a peak near the wavelength of 470 nm of the recording medium increased significantly in the force curves b and c where almost no fluorescence was observed.

The fluorescence intensity change rate (contrast) at a wavelength of 520 nm before and after UV irradiation was about 70 times.

In addition, FIG. 2 shows the relationship between the weight% of the specific example compound II-1 with respect to the acrylic resin and the fluorescence peak intensity and the fluorescence intensity change rate (contrast) before and after ultraviolet irradiation for 20 seconds.

[0109] An optical recording medium prepared in the same manner except that the acrylic resin was changed to an acrylic resin “Ovtrez OZ1100 (manufactured by Hitachi Chemical)” was irradiated with ultraviolet rays for 20 seconds, and then 80 ° C 85% RH Figure 5 shows the changes in peak intensity when stored at a high temperature and high humidity.

As is clear from these results, the optical recording medium using the optical recording material of the present invention is extremely excellent in the magnitude of the emission intensity change (contrast) and the storage stability of recorded information.

[0110] Further, using the same laser and optical system as those used for the evaluation of the two-photon absorption cross section, a laser beam having an average output of 45 mWZcm ² is condensed to about 1 mm in diameter, and an optical recording medium (acrylic resin) The recording layer of “Ataripet VH-5” was irradiated for 100 seconds. After that, place the optical recording medium in the box and irradiate it with UV light using a handy UV lamp (“AZUV“ SLUV-6 ”, main wavelength of irradiated light: 365 nm, intensity of irradiated surface: 0.05 mWZcm ² ) with the naked eye. As a result of the observation, a clear fluorescent spot with the same partial diameter as the beam diameter was confirmed.

[0111] Example 3

Preparation of optical recording media using the following specific example compound II 21 [Chemical 28]

(Specific compound Π— 21)

[0112] Visible absorption (max): 319nm (toluene)

Fluorescence emission peak wavelength (excitation wavelength: 325 nm): 380 nm (toluene)

[0113] An optical recording medium was prepared in the same manner as in Example 2 (using attalylic resin "Attalipetto VH-5") using Compound II-21 as an optical recording material. Figure 3 shows the fluorescence spectra before and after UV irradiation.

The two-photon absorption cross section of the specific example compound II-21 at a wavelength of 650 nm was 3 [GM].

In this optical recording medium, as in Example 2, almost no fluorescence was observed before the ultraviolet irradiation, but after the ultraviolet irradiation, the fluorescence emission intensity peaked at a wavelength of about 380 nm was significantly increased. The fluorescence intensity change rate (contrast) at a wavelength of 380 nm before and after UV irradiation was about 12 times.

[0114] Example 4

Preparation of optical recording media using the following specific example compound III 1

[Chemical 29]

(Specific compound IH-1) Visible absorption (max): 457nm (toluene)

Fluorescence emission peak wavelength (excitation wavelength: 325 nm): 550 nm (toluene) [0116] A specific example compound III-1 was used as an optical recording material, and a recording layer having a thickness of 10 m was prepared in the same manner as in Example 2 (using an acrylic resin “Ataripet VH-5”). An optical recording medium was prepared, and the fluorescence spectrum before and after UV irradiation is shown in Fig. 4.

The two-photon absorption cross section of the specific example compound III 1 at a wavelength of 650 nm was 5 [GM].

In this optical recording medium, fluorescence emission was observed before the ultraviolet irradiation! However, after the ultraviolet irradiation, the fluorescence emission intensity peaked at around 550 nm was greatly reduced. The fluorescence intensity change rate (contrast) at a wavelength of 550 nm before and after UV irradiation was about 8 times.

[0117] This application is based on a Japanese patent application (Japanese Patent Application No. 2006-1 41514) filed on May 22, 2006, which is incorporated by reference in its entirety.

Claims

The scope of the claims

[1] An optical recording material comprising a compound having a structure in which at least one luminescent group and one photolabile protecting group are bonded.

[2] The optical recording material according to [1], which has a compound strength having a structure represented by the following general formula (I):

[Chemical 1]

A—— (XB) n (I) In formula (I), A represents a luminescent group, X represents a divalent linking group, B represents a photolabile protecting group, n represents u is 1 It is an integer of ~ 6.

[3] The optical recording material according to [1], wherein the luminescent group has multiphoton absorption.

[4] The optical recording material according to [1], wherein the luminescent group is a fluorescent group.

5. The optical recording material according to claim 1, wherein the emission intensity increases after light irradiation.

6. The optical recording material according to claim 2, wherein the compound having a structure represented by the general formula (I) is a compound represented by the following general formula (II).

[Chemical 2]

Formula (π 冲,

a represents an integer of 1 to 3.

Z is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, or — (Ar ¹ ) — (X—B) (where Ar ¹ has a substituent, X represents a divalent linking group, B represents a photolabile protecting group, r and s are each independently 0 or 1, and R ¹ and Ar ¹ are bonded to each other. Which may form a 6-membered ring).

3. The optical recording material according to claim 2, wherein the compound having a structure represented by the general formula (I) is a compound represented by the following general formula (III).

[Chemical 3]

In formula (III),

X represents a divalent linking group,

B represents a photolabile protecting group,

t is an integer from 0 to 4, and u is an integer from 0 to 6.

3. The optical recording material according to claim 2, wherein the compound having a structure represented by the general formula (I) is a compound represented by the following general formula (IV).

[Chemical 4]

(IV)

Formula (IV 冲,

Y represents O— or S—

X represents a divalent linking group,

B represents a photolabile protecting group,

V and w are each independently an integer of 0 to 4.

The optical recording according to claim 2, wherein the photolabile protecting group B is any one selected from the group having the basic force represented by the following general formulas (V), (VI), (VII) and (VIII). Materials.

[Chemical 5]

R ⁹

-COOC-R ^10- …- _(Vffi)

R ¹¹ The aromatic ring of formulas (V) to (VII) may further have a substituent! /.

In the formula (VIII), R ⁹ , R ¹⁰ and R ¹¹ each independently represents an arbitrary substituent, and at least one of R ⁹ , R ¹⁰ and R ^] may have a substituent, It is an alkyl group.

An optical recording comprising the optical recording material according to claim 1 in a recording layer. Medium.

[11] Recording is performed by photo-dissociating a compound having a light-emitting group and a photo-dissociable protecting group constituting the optical recording material, and reproduction is performed by reading a change in emission intensity before and after photo-dissociation. 11. The recording / reproducing method for an optical recording medium according to claim 10, wherein the recording / reproducing method is performed.

[12] A compound represented by the following general formula (II):

[Chemical 6]

Formula (Π 冲,

X represents a divalent linking group,

a represents an integer of 1 to 3.

Z is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, or — (Ar ¹ ) — (X—B) (where Ar ¹ has a substituent, X represents a divalent linking group, B represents a group represented by the following general formula (V), (VI), (VII), or (VIII), and r and and each s independently represents 0 or 1, and R ¹ and Ar ¹ may combine to form a 6-membered ring.

[Chemical 7]

The aromatic ring of the formulas (V) to (VII) may further have a substituent V.

In the formula (Vm), R ⁹ , R ¹⁰ and R ¹¹ each independently represents an arbitrary substituent, but at least one of R ⁹ , R ¹⁰ and R may have a substituent, and may be an alkyl group. It is a group.