JP4151399B2 - Optical information recording medium - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is a write-once type optical information recording medium in a heat mode capable of recording and reproduction by 350 to 830 nm laser light such as CD-R, DVD-R, etc., wherein a recording layer is substituted with a metallocene compound substituent. The present invention relates to an optical information recording medium using a polymethine compound having a substituted substituent, and particularly improving light resistance.
[0002]
[Prior art]
As a means for recording and reproducing data such as images, images such as characters and graphics, video, or sound, a recording material capable of recording and reproducing corresponding to laser light with a wavelength of 770 to 830 nm, for example, contains a pentamethine cyanine dye. An optical disc having a recording layer is known as a CD-R. A DVD-R (digital video disc) capable of high-density recording and reproduction with a red laser beam having a shorter wavelength than this laser beam, for example, 620 to 690 nm. Recordable or digital versatile disc-recordable) has come to be used as a medium (optical information recording medium) that bears the future era replacing CD-R.
In such CD-R, DVD-R, etc., pits are formed by thermal decomposition in accordance with a signal of information to be recorded in response to a semiconductor laser having a wavelength of 600 to 800 nm, and recording is thereby performed. An organic dye compound that can be used for the recording layer is used to improve recording performance. In particular, cyanine dyes are excellent in that a highly productive method such as spin coating can be applied, and because of low thermal conductivity, local heating can be performed and pits with sharp edges and good dimensional stability can be formed. In particular, it has been attracting attention because of its high absorptivity and reflectivity in the wavelength range of semiconductor lasers.
[0003]
However, write-once optical information recording media such as CD-R and DVD-R generally do not have sufficient light resistance when a cyanine dye is used as the recording layer. It is easy to deteriorate due to sunlight, the recorded contents cannot be stored for a long time, and it is easy to deteriorate if the number of repetitions is increased by irradiating laser light during playback, and the reproducibility of images and sounds by playback There is a problem that the quality of the product is likely to be impaired.
As a countermeasure, a light stabilizer (quencher) such as a stabilizing radical is generally added to the main component of a cyanine dye having absorption characteristics in the semiconductor oscillation wavelength region, and this causes the dye to fade, for example. For example, singlet oxygen generated by sunlight is changed to mild triplet oxygen by its oxidizing action to improve the recording layer of the cyanine dye-containing layer of CD-R or DVD-R. If you want to keep a record of its contents, such as an encyclopedia, for a long time, it is not enough, but it also reduces the features of cyanine dyes that can be heated locally when such a light stabilizer is added. This causes so-called thermal interference, which adversely affects recording characteristics, and in particular causes deterioration in recording sensitivity and jitter.
In particular, in the future CD-R and DVD-R, in order to perform recording efficiently, it is demanded that the organic dye compound currently proposed as a dye for the recording layer can be recorded at high speed. However, in order to perform such high-speed recording, it is necessary to irradiate the recording layer with laser light and write it at high speed. For this purpose, the scanning speed of the laser light must be increased, As a result, the amount of energy per unit time required for writing is reduced, and when attempting to form a good pit as a signal of information to be written, the laser is irradiated to cover the reduction in the amount of energy. It is necessary to perform recording to form the pit with so-called high power to power up the light. In such a case, the addition of the above-mentioned light stabilizer to the cyanine dye tends to cause the above-mentioned thermal interference and the above-mentioned problem, and therefore a device for reducing the light stabilizer as much as possible is required.
As an improvement measure, as disclosed in JP-A-4-25493, an anion of an organometallic complex having a photostabilizing action is added to the cation of the cyanine dye main body, and both are integrated by ionic bonding. It is also one method to incorporate the light stabilizing component into the dye efficiently.
[0004]
[Patent Document 1]
JP-A-4-25493 (pages 630-631)
[0005]
[Problems to be solved by the invention]
However, the dye molecules obtained as a result of the integration become large, the ratio of the cyanine dye main body to the dye molecules becomes relatively small, and the molecular extinction coefficient decreases. In order to achieve better light stabilization, the anionic molecule of an organometallic complex has to be large in the past, but the larger the molecule, the more the molecular extinction coefficient becomes. It tends to decrease. As a result, it is still insufficient to solve the problems caused by thermal interference as described above.
In particular, cyanine dyes, azo dyes, or phthalocyanine compounds used in current CD-Rs and DVD-Rs are still in a situation where the above-mentioned high-speed recording cannot be sufficiently handled. In addition, because the output power of the semiconductor laser itself is limited, even if the energy for writing is reduced in response to high-speed recording, the semiconductor laser unit can form good pits with the reduced energy. There is a need for highly sensitive recording materials with high reactivity per energy.
[0006]
A first object of the present invention is to provide an optical information recording medium that can prevent photothermal interference deterioration during storage for a long period of time or reproduction with a large number of repetitions and that does not impair the performance of recording and reproduction.
A second object of the present invention is to provide an optical information recording medium that reduces the light absorption energy itself of the recording compound in the heat mode and prevents its deterioration.
It is a third object of the present invention to provide an optical information recording medium that does not require the addition of stabilizing radicals, quenchers or other light stabilizers.
A fourth object of the present invention is to provide an optical information recording medium using a recording compound having a high reactivity with a laser beam selected from a wavelength range of about 350 nm to 830 nm.
A fifth object of the present invention is to provide an optical information recording medium having good recording sensitivity with respect to a laser beam selected from a wavelength range of about 350 nm to 830 nm.
A sixth object of the present invention is to provide an optical information recording medium capable of performing good high-speed recording with respect to a laser beam selected from a wavelength range of about 350 nm to 830 nm.
The seventh object of the present invention is to provide an optical information recording medium in which a recording compound having good solubility in a solvent can be used.
An eighth object of the present invention is to provide an optical information recording medium in which a recording compound having good film forming properties can be used.
A ninth object of the present invention is to provide an optical information recording medium to which the conventional manufacturing method of CR-R and DVD-R can be applied almost without major changes.
[0007]
[Means for Solving the Problems]
  As a result of diligent research to solve the above-mentioned problems, the present inventors have, for example, cyanine dyes (metallocene-introduced cyanine dyes) into which a substituent having a metallocene substituent is introduced have excellent light resistance and a wavelength of about 350 nm to An optical information recording medium provided with a light interference layer having a dye layer containing the dye layer can form good pits because the dye layer containing the dye has high reactivity with respect to 830 nm laser light. It has been found that this has been achieved and has led to the present invention. The present invention relates to (1) an optical information recording medium having a light interference layer including a recording layer on a substrate.Is belowRepresented by the general formula [Chemical Formula 10]To cyanine compoundsIntroducing a spiro fused ring,AndIntroducing a substituent having a substituent of a metallocene compound into N of the heterocyclic ringTableCyanine compoundIncludingAn optical information recording medium is provided.
[Chemical Formula 10]
(However,, N ⁺X^-Represents the same as N—X in a different notation, and C1 and C2 both represent either a spiro-fused ring, and when either one represents a spiro-fused ring, the other represents dimethyl,^-Is a halogen atom, PF₆ ^-, Perchloric acid, borohydrofluoric acid, phosphoric acid, benzenesulfonic acid, SbF₆ ^-, Toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-Represents an anion selected from the group of anions obtained by anionizing a metal complex such as a dithiol complex or a metallocene compound.And M ₁, M₂Represents a substituent of a metallocene compound or a hydrogen atom, R₁-M₁, R₂-M₂Is a substituted or non-substituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl which may have another substituent substituted with a substituent of a metallocene compound. Group, halogenated alkyl group, alkyl hydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkyl A sulfonyl group, an alkyl carboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl group and a phenoxyalkyl group (the benzene ring portion and / or the hydrogen atom of the alkyl portion It may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom, and the same applies to the corresponding part of the phenyl group, benzyl group, and alkylphenyl group. When both have a substituent substituted with a substituent of a metallocene compound, they may be the same or different, and only one of them has a substituent substituted with a substituent of a metallocene compound The other is a substituted or unsubstituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, halogenated alkyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkyl other than the substituent of the metallocene compound. Amide group, alkylamino group, alkylsulfonamide group, alkylcarba Yl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkylsulfonyl group, alkyl carboxyl group or alkylsulfonyl group bonded to metal ion or alkyl group, phenyl group, benzyl group, alkylphenyl group and phenoxyalkyl Group (the hydrogen atom of the benzene ring portion and / or the alkyl portion may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom. The same applies to the corresponding part.) Represents a substituent selected from the group ofAnd R _Three, R_FourBoth represent hydrogen atoms, and both or one of them represents a substituent having a substituent of a metallocene compound, and both of them may be the same or different, and in either case, the other is a hydrogen atom Or an organic substituent other than a substituent having a substituent of a metallocene compound, R_Three, R_FourAre each a hydrogen atom, a substituent having a substituent of a metallocene compound, and a plurality of the same or different substituents selected from organic substituents other than a substituent having a substituent of a metallocene compound (any position where substitution is possible) But it's okay)A1, A2 represents a substituted or unsubstituted benzene ring or naphthalene ringAnd insideN of the polymethine chain of the central linking chain represents a positive integer including 0, and the polymethine chain may have a substituent or may have a cyclic side chain extending between a plurality of carbons. )
  The present invention also provides (2),Of metallocene compoundsThe molecular weight of the substituent having the substituent isCyanine(1) optical information recording medium having a molecular weight smaller than that of the compound;3), R₁And R₂Is C_nH_2n, N is 0-8, and may be the same or different (1) or (2)Optical information recording media, (4), X^-Is ClO_Four ^-, PF₆ ^-- OrBF _Four ^- soAbove ((1) One of (3)Optical information recording media, (5), Wherein the metallocene compound is a compound represented by the following general formula [Formula 15]1) One of (4)Optical information recording medium,
Embedded image
  (M represents a metal atom, R¹, R²Represents a substituent. )
(6), M is Fe, Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr, Lu, W, Os or Ir, and R¹, R²Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group thereof, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aroyl group having 7 to 10 carbon atoms, 1 to 1 carbon atom An aldehyde group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 10 carbon atoms, a hydroxyl group, a halogen atom, a boric acid group, a benzoyl group, and an alkenyl group having 2 to 10 carbon atoms, including a lower alkenyl group, A hydroxyalkyl group, an acetyl group, an aliphatic cyclic group or an alkoxycarbonyl group (each of which may have a substituent), which may be the same or different (5) Optical information recording medium, (7), R₁-M₁And R₂-M₂At least one of the above has a branched side chain (1) Or (6) Any optical information recording medium, (8), And the optical interference layer can be recorded and reproduced by a laser beam selected from a wavelength region of around 350 nm to 830 nm.1) Or (71) an optical information recording medium.
  In addition, "The present invention relates to (1) an optical information recording medium having a light interference layer including a recording layer on a substrate, wherein the recording layer has a substituent having a substituent of an organometallic complex comprising a cation component and an anion component. The present invention provides an optical information recording medium containing a substituted polymethine compound introduced into the cation component of the compound.
  The present invention also provides (2) the optical information recording medium of (1), wherein the molecular weight of the substituent having a substituent of the organometallic complex is smaller than the molecular weight of the polymethine compound, (3), and the organometallic complex is a metallocene In the optical information recording medium of (1) or (2), which is a compound, (4), an optical information recording medium having a light interference layer including a recording layer on a substrate, the recording layer has a substituent of a metallocene compound. An optical information recording medium containing a substituted polymethine compound obtained by introducing a substituted polymethine compound into the anion component of a polymethine compound composed of a cation component and an anion component, and the polymethine compound is at least a cyanine compound and a merocyanine compound One type of the optical information recording medium according to any one of (1) to (4), (6), a cyanine compound represented by the following general formula [Chemical Formula 1] An emission-based compound, a merocyanine-based compound is a merocyanine compound represented by the following general formula [2] The optical information recording medium of the above (5),
[Chemical 1]
[Chemical 2]
(However, A is
[Chemical 3]
And B is
[Formula 4]
A ′ represents
[Chemical formula 5]
And B ′ is
[Chemical 6]
In the case where each of A, B, A ′ and B ′ has an aromatic ring, it may have a halogen atom, an alkyl group, an alkoxy group or an aryl group as one or a plurality of substituents, Represents an alkyl group or a sulfonated alkyl group, and each of (A, B) and (A ′, B ′) may be the same as or different from each other, and X represents an anion (the sulfonated group described above). The alkyl group may have X), N to which X of A and A ′ is bonded represents a cation, and X is bonded to R of B and B ′. When N is a cation, it may be bonded to this, in which case each N in A and A ′ is a non-ion to which only R is bonded, R ′ represents a hydrogen atom or a carboalkyl group, and R ″. Represents a hydrogen atom or an alkyl group, R ′, '' May be the same or different, may be interchanged, n of the polymethine chain of the central linking chain represents a positive integer including zero. )
(7) The optical information recording medium of (5) or (6) above, wherein the cyanine compound is a cyanine compound represented by the following general formula [Chem.
[Chemical 7]
(However, A1, A2 represents a substituted or unsubstituted benzene ring or naphthalene ring, Y, Y ′ represents C, —CH═CH—, O, S, Se, or NH, and may be the same or different. When it can have a substituent, the substituent may be an alkyl group, Y and Y ′ are both or any one of C, and at least one C has a spiro-fused ring, When only one has a spiro-fused ring, the other C substituent may be a dialkyl group, and R₁, R₂Represents an alkyl group or a sulfonated alkyl group, X is a halogen atom, PF₆ ^-, Perchloric acid, borohydrofluoric acid, phosphoric acid, benzenesulfonic acid, SbF₆ ^-, Toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-Represents an anion selected from the group of anions of tetraphenylboric acid and tungstic acid (wherein the sulfonated alkyl group may have X), N in the heterocyclic ring represents a cation, while X represents R in the other heterocyclic ring.₂When N to which is bonded is a cation, it may be bonded to this, in which case N in the above one heterocyclic ring is R₁The polymethine chain n in the central linking chain represents a positive integer including 0, and the polymethine chain may have a substituent, and a cyclic side chain extending between a plurality of carbons. You may have. ), (8), a substituted group having a substituent of a metallocene compound is introduced into the cation component of the above general formula [Chem. 7] to obtain a substituted cyanine compound, and the substituted cyanine compound is represented by the following general formula [Chem. The optical information recording medium according to (7) above, which is a substituted cyanine compound in which a substituent having a substituent of a metallocene compound is introduced into the aromatic ring of the heterocyclic ring represented by
[Chemical 8]
(However, X^-May be a monovalent or divalent anion obtained by introducing an anionic group into an organometallic complex such as a dithiol complex or a metallocene compound, and R_Three, R_FourEach symbol other than represents the same as in the above general formula [Chem. 7]_Three, R_FourBoth represent hydrogen atoms, and both or one of them represents a substituent having a substituent of a metallocene compound, and both of them may be the same or different, and in either case, the other is a hydrogen atom Or an organic substituent other than a substituent having a substituent of a metallocene compound, R_Three, R_FourAre each a hydrogen atom, a substituent having a substituent of a metallocene compound, and a plurality of the same or different substituents selected from organic substituents other than a substituent having a substituent of a metallocene compound (any position where substitution is possible) It may be). ), (9), a substituted group having a substituent of a metallocene compound is introduced into the cation component of the above general formula [Chem. 7] to obtain a substituted cyanine compound, and the substituted cyanine compound is represented by the following general formula [Chem. 9] The optical information recording medium of (7) above, which is a cyanine compound obtained by introducing a substituent having a substituent of a metallocene compound into N of the heterocyclic ring represented by
[Chemical 9]
(However, R_Three, R_FourBoth may be hydrogen atoms and R₁-M₁, R₂-M₂Except for, each symbol, etc. represents the same as that in the above general formula [Chemical Formula 8]₁, M₂Represents a substituent of a metallocene compound or a hydrogen atom, R₁-M₁, R₂-M₂Is a substituted or non-substituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl which may have another substituent substituted with a substituent of a metallocene compound. Group, halogenated alkyl group, alkyl hydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkyl A sulfonyl group, an alkyl carboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl group and a phenoxyalkyl group (the benzene ring portion and / or the hydrogen atom of the alkyl portion It may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom, and the same applies to the corresponding part of the phenyl group, benzyl group, and alkylphenyl group. When both have a substituent substituted with a substituent of a metallocene compound, they may be the same or different, and only one of them has a substituent substituted with a substituent of a metallocene compound The other is a substituted or unsubstituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, halogenated alkyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkyl other than the substituent of the metallocene compound. Amide group, alkylamino group, alkylsulfonamide group, alkylcarba Yl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkylsulfonyl group, alkyl carboxyl group or alkylsulfonyl group bonded to metal ion or alkyl group, phenyl group, benzyl group, alkylphenyl group and phenoxyalkyl Group (the hydrogen atom of the benzene ring portion and / or the alkyl portion may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom. The same applies to the corresponding portion.) Represents a substituent selected from the group of ), (10), a substituted cyanine compound obtained by introducing a substituent having a substituent of a metallocene compound into N of the heterocyclic ring represented by the above general formula [Chemical Formula 9] is represented by the following general formula [Chemical Formula 10]. (9) the optical information recording medium, which is a substituted cyanine compound into which a spiro-fused ring is introduced,
[Chemical Formula 10]
(However, N⁺X^-The symbols other than C1, C2, and the like represent the same as those in the above general formula [Chemical Formula 9], N⁺X^-Represents the same as N—X in a different notation, and C1 and C2 both represent either a spiro-fused ring, and when either one represents a spiro-fused ring, the other represents dimethyl,^-Is a halogen atom, PF₆ ^-, Perchloric acid, borohydrofluoric acid, phosphoric acid, benzenesulfonic acid, SbF₆ ^-, Toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-Represents an anion selected from the group of anions obtained by anionizing a metal complex such as a dithiol complex or a metallocene compound. ), (11), R₁And R₂Is C_nH_2n, N is 0-8, and may be the same or different, (9) or (10) optical information recording medium, (12), R₁-M₁And R₂-M₂At least one of the optical information recording media of the above (10) or (11) having a branched side chain, (13), X^-Is ClO_Four ^-, PF₆ ^-, BF_Four ^-Alternatively, the optical information recording medium of any of (9) to (12) above, which is an anion obtained by anionizing a metallocene compound, (14), wherein the metallocene compound is represented by the following general formula [Chemical Formula 15] An optical information recording medium according to any one of (2) to (13),
Embedded image
  (M represents a metal atom, R¹, R²Represents a substituent. ), (15), M is Fe, Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr, Lu, W, Os or Ir, and R¹, R²Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group thereof, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aroyl group having 7 to 10 carbon atoms, 1 to 1 carbon atom An aldehyde group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 10 carbon atoms, a hydroxyl group, a halogen atom, a boric acid group, a benzoyl group, and an alkenyl group having 2 to 10 carbon atoms, including a lower alkenyl group, (14) the optical information recording medium of (14), which represents a hydroxyalkyl group, an acetyl group, an aliphatic cyclic group or an alkoxycarbonyl group (each may have a substituent), and may be the same or different; The optical information recording according to any one of (1) to (15), wherein the optical interference layer can be recorded and reproduced by a laser beam selected from a wavelength region of about 350 nm to 830 nm. It is intended to provide the body.It can also be said.
[0008]
In the present invention, the optical interference layer is formed so that recording and reproduction can be performed by a laser beam selected from a wavelength region of about 350 nm to 830 nm, which is in the range of about 640 nm to 680 nm. It is intended to be usable for DVD-R for laser light and for CD-R for laser light in the range of about 770 nm to 830 nm. In the future, it will also be applicable to so-called blue laser compatible media for lasers of around 400 nm.
The optical interference layer is composed of a dye layer made of an organic dye material, a layer made of another organic material or an inorganic material, a recording layer including a single layer or a plurality of dye layers capable of forming a pit by laser light irradiation, In addition to this recording layer, the refractive index and the film thickness are adjusted for the purpose of adjusting the optical properties of the optical information recording medium, for example, an enhancement layer made of a resin material, and in the case where there are a plurality of substrates, a dye layer, and a dye layer, The intermediate layer etc. which are provided in are included, and these are generic names. The “dye layer made of an organic dye material” may be a “recording layer containing an organic material”, and the organic material is not limited to an organic dye material, and an uncolored material may be used, and the dye layer is also colored. However, it may be referred to as a dye layer including the case where it is not colored for convenience.
[0009]
As the substituted polymethine compound in which a substituent having an organometallic complex substituent is introduced into the polymethine compound to be contained in the above dye layer, as the polymethine compound is also known as a polymethine dye, a cation is used. A compound in which a component and an anion component are combined, but a compound in which a substituent having a substituent of the organometallic complex is introduced into the cation component is not known. In this case, the anion component conventionally used can be used including an anion of an organometallic complex, but in the case of a cyanine dye, for example, it is used as a quencher anion to improve light resistance. Since there are also anions of organometallic complexes that are used, when introducing a substituent having a substituent of the organometallic complex only into the anion component, the organometallic complex is limited to a metallocene compound.
The molecular weight of the substituent having a substituent of the organometallic complex is preferably smaller than the molecular weight of the polymethine compound into which the organometallic complex is introduced, but this is also preferable because it does not impair the solubility in the solvent, the absorbance, etc. Metallocene compounds are preferred because of their relatively low molecular weight among organometallic complexes.
[0010]
Examples of the polymethine compound include a cyanine compound represented by the above general formula [1] and a merocyanine compound represented by the above general formula [Chemical Formula 2], and it is preferable to use at least one of these compounds. As the cyanine compound, a compound represented by the above general formula [Chemical Formula 7] is more preferable. In these general formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 7], a substituted cyanine compound in which a substituent substituted with a substituent of the metallocene compound is introduced is preferable. Any of these may be used, and the number and type thereof are not limited, and examples thereof include substituted cyanine compounds of the above general formulas [Chemical Formula 8] and [Chemical Formula 9].
[0011]
Examples of the substituted cyanine compounds belonging to the above general formula [Chemical Formula 8] include compounds represented by the following general formula [Chemical Formula 11] and the following general formula [Chemical Formula 12].
Embedded image
Embedded image
(However, R₁, R₂, X^-And n are the same as those in the above general formula [Chemical Formula 8], and M is a metal of Fe, Ni, or Co. )
In addition to the above compound, a compound in which the anion component in the above [Chemical Formula 11] is used in place of the anionic component in the above [Chemical Formula 12], and the anion component in the above [Chemical Formula 11] or in place of the anionic component^-And a compound having a metallocene-based compound substituent on one naphthalene ring.
While these compounds have the effect of improving light resistance, the compound of [Chemical Formula 11] has an advantage that it can be used by appropriately changing the cation component of the cyanine compound.
[0012]
Examples of the substituted cyanine compound belonging to the general formula [Chemical Formula 9] include compounds represented by the following general formula [Chemical Formula 13] and the following general formula [14].
Embedded image
Embedded image
(Wherein n represents 0, 1 or 2, m and m 'are 1 to 8, and may be the same or different, and X^-Is ClO_Four ^-, PF₆ ^-, BF_Four ^-Or SbF₆ ^-M represents Fe, Ni or Co metal, R_Five, R₆Represents an alkyl group such as a lower alkyl group, which may be the same or different, and R₇, R₈Represents a hydrogen atom or an alkyl group such as a lower alkyl group, which may be the same or different. )
The compounds of the above [Chemical Formula 13] and [Chemical Formula 14] can improve the light resistance, and the compound of the above [Chemical Formula 13] has m and m ′ of 1 to 8, thereby increasing the length of the alkyl group. , The solubility in a solvent can be improved. Especially when n is 2, pentamethine (a dye for CD-R), and when M is Fe, the effect of improving the solubility is large. . In addition, the compound [14] described above can improve the decomposability when irradiated with laser light by having a branched alkyl chain, and can improve the sensitivity when used in the recording layer. In particular, when n is 1, trimethine (a dye for DVD-R), and when M is Fe, the effect of improving the decomposability is great.
[0013]
The compound belonging to the above general formula [Chemical Formula 9] belonging to the above general formula [Chemical Formula 9] is a substituted cyanine compound into which a spiro fused ring is introduced (a spiro fused ring introduced type substituted cyanine compound). Spiro-fused ring is a stereocyclic optically active substance due to molecular asymmetry in the bicyclic compound spirane sharing one carbon, but the cyclic group of the cyanine compound is made one side, and the cyclic group is constituted. This is the other cyclic group (spiro ring structure) that shares the carbon to be used as the carbon constituting the other cyclic group, and this spiro-fused ring-introduced cyanine compound is an optical activity of stereoisomers due to molecular asymmetry. Is the body.
In the general formula [Chemical Formula 10], it is preferable from the standpoint of sensitivity to laser light that one of C1 and C2 represents a spiro fused ring and the other represents dimethyl, but both of them represent a spiro fused ring. The spiro-fused ring may be the same or different. Examples of the spiro-fused ring include a 6-membered ring (C (carbon) is a 6-membered ring, the same applies hereinafter), a 5-membered ring, and a 3-membered ring. The same applies to the above general formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 7] to [Chemical Formula 9]. When n is 0, it is a monomethine cyanine dye. Cyanine dye, when n is 2, it is a pentamethine cyanine dye and can be used alone or in combination with other dyes as a dye for DVD-R, CD-R, etc. As a dye for CD-R, a trimethine cyanine dye or the like is preferably used as a dye for DVD-R.
[0014]
The spiro-fused ring-introduced cyanine compound is a compound represented by the general formula [Chemical Formula 10], for example, when a spiro-fused ring is introduced into both due to the structure of the stereoisomer due to molecular asymmetry described above. Can be a symmetrical structure, in which case R in the general formula [Chemical Formula 10]₁-M₁, R₂-M₂Are the same, and the present invention also includes this case.₁-M₁, R₂-M₂As a matter of course, when a spiro-fused ring is introduced into only one of them, a left-right asymmetric structure can be obtained. Such a spiro-fused ring-introduced cyanine compound having a left-right asymmetric structure is preferable in terms of solubility in a solvent and film formability.
R in the general formula [Chemical Formula 10]₁-M₁, R₂-M₂Specifically, the corresponding substituents in the compounds of the above [Chemical Formula 13] and [Chemical Formula 14] are mentioned, and as described above, the solubility in a solvent is improved and the decomposability to laser light is improved. Especially when the former is pentamethine (dye for CD-R) and M is Fe, the latter is trimethine (dye for DVD-R) and when M is Fe, the respective improvement effects Can be increased. In the general formula [Chemical Formula 10], R_Three, R_Four, N⁺Substituent, N substituent, X^-In addition, specific compounds having the corresponding substituents of the above-mentioned [Chemical Formula 11] and [Chemical Formula 12] and similar compounds thereof can also be mentioned, and the same merit can be obtained.
[0015]
In the recording layer containing the above spiro-fused ring-introduced cyanine compound, the sensitivity, that is, the reactivity with respect to the given energy, for example, the thermal decomposability is increased. In the case of compounds, the spirocyclic structure, which is unstable as a molecular structure, is directly introduced into the terminal heterocyclic ring of the cyanine dye, resulting in the stereoisomer structure due to the above-mentioned molecular asymmetry, and the entire cyanine molecule is unstable. It can be considered that the structure (non-planar structure) allows the molecule to be distorted due to, for example, stericization by introduction of a spiro-fused ring, and changes such as decomposition are easily caused by heat.
For compounds belonging to the above general formula [Chemical Formula 10], not only when the spiro-fused ring is a 6-membered ring, but also in the case of other above-mentioned cyclic groups, structural optimization calculation in molecular simulation is performed to obtain a spiro ring structure. The relationship of the reactivity to energy applied to the recording layer containing the spiro-fused ring-introduced cyanine dye described above is obtained when the spiro-fused ring is a 6-membered ring. This was consistent with the actual characterization performed so far.
[0016]
Thus, it is possible to increase the thermal decomposability of organic dyes in terms of their molecular structure, lower the thermal decomposition temperature to increase the reactivity to laser light, and improve the so-called sensitivity. By using this organic dye in a dye layer such as -R, the sensitivity of recording with laser light can be improved without affecting the reflectance with respect to the laser light, that is, the sensitivity of reproduction. This means that if a spiro-fused ring is introduced for a cyanine dye that has excellent reflectivity with respect to laser light, it becomes easier to improve the sensitivity of recording without losing the reflectivity, and the selection range of high-speed recording materials can be expanded. Can do. In contrast, in optical information recording media using conventional organic dyes, when considering a recording material corresponding to high-speed recording, a material having better absorption at the recording wavelength is selected. In order to improve the amount of light absorption in the region, the absorption peak (λ_maxHowever, when a material on the long wavelength side is selected, there is a problem in that the absorption at the reproduction wavelength increases and the reflectance cannot be secured, and the reproduction sensitivity cannot be improved. The present invention also has an advantage that this problem can be easily solved.
In addition, it is a compound belonging to the above general formula [Chemical Formula 10], and R₁-M₁, R₂-M₂M in₁, M₂About the specific compound whose is a hydrogen atom, the manufacture and identification are performed.
[0017]
In the above general formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 7] to [Chemical Formula 10], in the explanation of the respective general formulas, the substituents having the substituent of the metallocene compound are also described. However, the “substituent having a substituent of the metallocene compound” may be the substituent itself of the metallocene compound, and in any case, the metallocene compound is a compound represented by the above general formula [Chemical Formula 15] Can be mentioned. In this general formula, M represents a metal, particularly a metal such as Fe as described above. Of course, M is not only at room temperature, but also thermally stable when irradiated with a laser and heated to a relatively high temperature. Ferrocene (Fe biscyclopentadienyl complex), ruthenocene, osmocene, nickelocene, titanocene, etc., and their derivatives, when recorded by laser irradiation, the formed pit shape is made uniform, and the pit edge shape is centered on the pit. The optical information recording medium having a recording layer containing each compound is very good from the viewpoint of durability. R¹, R²As specific metallocene compounds, for example, when the metal is Fe, the following ferrocene compounds of the following [Chemical Formula 16] can be exemplified. Among them, alkyl group, acyl group, and benzoyl group-substituted metallocene compounds are preferable from the viewpoints of solubility and sublimation resistance. When these ferrocene compounds are used as substituents, the substitution position may be the ferrocene nucleus itself, or may be the substituent, and the same applies to other metallocene compounds.
[0018]
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[0019]
In order to obtain a compound substituted with a substituent having a substituent of a metallocene compound, for example, the cyanine compound can be produced by, for example, the following reaction formulas [Chemical Formula 17] and [Chemical Formula 18]. Compounds belonging to the formulas [Chemical Formula 1], [Chemical Formula 2], [Chemical Formula 7] to [Chemical Formula 10] can also be produced according to this.
[0020]
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[0021]
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[0022]
In the reaction formula, (a) and (b) can be produced by known methods, from which (c) can be produced by heating, and from this (c) and diphenylformamidine, (d) is produced by heating. This (d) can be changed to Ac₂(E) can be prepared by acetylation with O (acetic anhydride), and then (a) can be reacted in the presence of triethylamine to produce (f), and finally to obtain the desired anion component, for example HPF₆The target product (g) can be obtained by converting the kind of anion component. From this reaction formula, it can be seen that (c) to (g) can be produced using existing substances from (a) and (b), but when (a) is reacted again to obtain (f), If (c) is used instead of (a), the N substituents on both sides of the methine chain in (f) can be made the same. In this case, instead of (c), the alkyl iodide group of (b) The length of the alkyl group of the N substituent on both sides of the methine chain in (f) can be obtained by using the ferrocene derivative in which the length of the alkyl group is changed and the compound corresponding to (c) obtained by using (a). Are obtained. Similarly, instead of (c), this corresponds to (c) obtained by using (a) and (a) a ferrocene derivative using an alkyl group branched to the alkyl group of the alkyl iodide group of (b). When a compound is used, a compound in which an alkyl group is branched to N substituents on both sides of the methine chain in (f) is obtained. In (a) to (g), a substituent having a ferrocene substituent or a ferrocene substituent can be introduced by reacting, for example, a halogenated alkyl group-substituted ferrocene such as (b) with an aromatic ring. . At that time, if an alkyl halide is used as the component (b), the N substituents on both sides of the methine chain can be converted to alkyl groups in (f) and (g). In addition, if a component having a spiro condensed ring is used as component (a) to be reacted twice, a compound having a spiro condensed ring on one or both sides of the methine chain in (f) and (g) is obtained. Can do. When obtaining (g), HPF₆By using a compound of an anionic component into which a substituent having a ferrocene substituent is introduced instead of, a compound having an anionic component into which a substituent having a ferrocene substituent is introduced in (g) can be obtained. Thus, by using each of the above reactions, the substituent having a ferrocene substituent is changed to at least one of N substituents on both sides of the methine chain, at least one of the aromatic rings on both sides of the methine chain of the cation component, or an anionic component. A wide variety of compounds combining these can be obtained.
[0023]
Examples of the cyanine compound or merocyanine compound that can be substituted with a substituent having a metallocene substituent in accordance with the above can also include the following compounds [Chemical Formula 19] to [Chemical Formula 24].
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[0024]
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[0025]
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[0026]
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[0027]
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[0028]
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Here, for example, for the first compound of [Chemical Formula 19], when the ethyl group of at least one N substituent on both sides of the methine chain has a substituent of a metallocene compound, at least one of the both sides of the methine chain In the case where the benzene ring has a substituent of a metallocene compound or a substituent having the substituent, at least one in the case of having an anion component substituted with a substituent of the metallocene compound or a substituent having the substituent instead of Br There are two cases. The same applies to other compounds.
Specifically, the following [Chemical Formula 25] to [Chemical Formula 35] can be mentioned in addition to those shown in the Examples described later.
[0029]
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[0030]
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[0031]
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[0032]
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[0033]
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[0034]
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[0035]
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[0036]
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[0037]
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[0038]
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[0039]
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[0040]
In addition, about the said compound, the thing of the thing of the trimethine made into the pentamethine and the thing of the pentamethine made into the trimethine is also mentioned.
In the optical interference layer of the present invention, the above general formulas [Chemical Formula 1], [Chemical Formula 2], [Chemical Formula 7] to [Chemical Formula 10], the above compounds [Chemical Formula 11] to [Chemical Formula 14], ] Substitution of a metallocene compound into (f), (g) obtained in [Chemical Formula 18], other compounds according to this, and the compounds in [Chemical Formula 19] to [Chemical Formula 24] obtained in accordance with this reaction formula In addition to the compounds belonging to each of which a substituent having a group is introduced, the compounds having a substituent having a substituent of each metallocene compound are excluded, that is, a compound having a substituent such as a hydrogen atom in place of the substituent, etc. One or more of these compounds or dyes may be used together by providing the same dye layer or other dye layer, and a compound in which a substituent having a substituent of a metallocene compound in all the compounds or in all the dyes is introduced At least 50 wt%, i.e. when using 50 wt% or more, it is possible to achieve better described effect by using a compound or dye etc. metallocene compound is introduced to the sensitivity of recording by laser is improved. In this case, if the methine chains having the same number are mixed, for example, in the case of a trimethine chain compound, it is preferable for a DVD-R, and in the case of a pentamethine chain compound, it is preferable for a CD-R.
As other compounds or dyes described above, a cyanine compound (cyanine dye) represented by the following general formula [Chemical Formula 36] is used in all compounds or in all dyes at most 50% by weight, that is, 50% by weight or less. Also good.
[0041]
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[However, A represents any one of the following general formulas [Chemical Formula 37] to [Chemical Formula 39],
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,
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,
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,
A ′ represents any one of the following general formulas [Chemical Formula 40] to [Chemical Formula 42],
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,
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,
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,
A and A 'may be the same or different (provided that D and D'₁, D₂Are a hydrogen atom, alkyl group, alkoxyl group, hydroxyl group, halogen atom, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, Alkylcarbamoyl group, alkylsulfamoyl group, alkylsulfonyl group, phenyl group, cyano group, ester group, nitro group, acyl group, allyl group, aryl group, aryloxy group, alkylthio group, arylthio group, phenylazo group, pyridinoazo group Alkylcarbonylamino group, sulfonamido group, amino group, alkylsulfone group, thiocyano group, mercapto group, chlorosulfone group, alkylazomethine group, alkylaminosulfone group, vinyl group and sulfone It represents a substituent selected from among the group of radicals may be heterologous be homologous, p, q each represents 1 or more integer a number of substituents. ), R_Three, R_Four Is a substituted or unsubstituted alkyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, alkoxyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, Alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, halogenated alkyl group, alkylsulfonyl group, alkylcarboxyl group or alkylsulfolinyl group bonded to metal ion or alkyl group, phenyl group, benzyl group, alkylphenyl Group and phenoxyalkyl group (the hydrogen atom of the benzene ring portion and / or the alkyl portion may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, a halogen atom, etc. Phenyl group, a benzyl group, is the same for the corresponding portion of the alkyl phenyl group.) Represents a substituent selected from the group of may be the same or different, X^-And n are the same as those in the above general formula [Chemical Formula 1]. ]
In the above general formula [Chemical Formula 36], A is arbitrarily selected from the general formulas of the above General Formulas [Chemical Formula 37] to [Chemical Formula 39], and A ′ is selected from the general formulas of the above Formulas [Chemical Formula 40] to [Chemical Formula 42] Randomly selected and both individual compounds of each selected individual are included. For example, a combination of the general formula [Chemical Formula 37] and each of the general formulas [Chemical Formula 40] to [Chemical Formula 42] can be mentioned, but the same applies to the other general formulas [Chemical Formula 38] and [Chemical Formula 39]. Substituents for A and A ′ (D₁) P, (D₂) P and q of q are at least 1, but are a plurality of integers, that is, an integer of 2 or more.
As a method for synthesizing the dye, the method described in The Chemistry of Synthetic Dies Vol 14 can be used.
[0042]
In the compounds of the above general formulas [Chemical Formula 1], [Chemical Formula 2], [Chemical Formula 7] to [Chemical Formula 10], and [Chemical Formula 11] to [Chemical Formula 14], in particular, the above general formulas [Chemical Formula 7] to [Chemical Formula 10]. (F) and (g) obtained in the above [Chemical Formula 11] to [Chemical Formula 14] and the above reaction formulas [Chemical Formula 17] and [Chemical Formula 18] and other compounds equivalent thereto, and obtained in accordance with this reaction formula. In the compounds of the above [Chemical Formula 19] to [Chemical Formula 24], the above [Chemical Formula 25] to [Chemical Formula 35] and the compounds used in the examples described below, each of the compounds belonging to each is used alone, or further substituted with a metallocene compound. In the case where one or a plurality of other compounds or dyes other than the compound having a substituent having a group introduced are used in combination with the same dye layer or other dye layers, these compounds or dyes may be used alone. Good, light stable to improve light resistance Agent may be used is contained in is contained in the dye layer or another layer, the.
Examples of such light stabilizers include metal complexes, and examples of the metal complexes include compounds represented by the following general formula [Chemical Formula 43].
[0043]
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[However, R¹, R²Are a halogen atom, a phenyl group, an alkyl group, a cyano group, a thioalkyl group, an alkylsulfonyl group, r and s each represent an integer of 1 to 4,^FourRepresents an alkyl group, Y represents N or P, and M represents a metal such as Cu, Co or Ni. ]
[0044]
Specific compounds belonging to the above general formula [Chemical Formula 41] include the following [Chemical Formula 44] and [Chemical Formula 45] compounds.
[0045]
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[0046]
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[0047]
Examples of the light stabilizer include aminium-based and diimonium-based stabilizers. Specific examples of the compound include compounds represented by the following [Chemical Formula 46] and [Chemical Formula 47].
These light stabilizers can be used in at least one kind, that is, alone or in combination.
[0048]
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[0049]
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[0050]
In order to produce the optical information recording medium of the present invention, a polymethine compound into which a substituent having a substituent of the organometallic complex is introduced, for example, a compound represented by the above general formula [Chemical Formula 1], or this and other cyanines A mixed dye in which a compound or the like is dissolved (the former is preferably mixed at 50% by weight or more), or a solution in which a metal complex represented by the above general formula [Chemical Formula 43] or other light stabilizer is dissolved in each of them. Prepare and apply to translucent substrate. For these dye solutions, fluorine solvents such as chloroform, dichloroethane, fluorinated alcohol, methyl ethyl ketone, dimethylformamide, methanol, toluene, cyclohexanone, acetylacetone, diacetone alcohol, cellosolves such as methyl cellosolve, dioxane, etc. can be used. These may be used in combination. The mixing ratio of the cyanine dye in these cases is preferably 1% by weight to 10% by weight.
Examples of the substrate used in the present invention include plastics such as glass, epoxy resin, methacrylic resin, polycarbonate resin, polyester resin, polyvinyl chloride resin, and polyolefin resin. This substrate may be formed with track grooves or pits and may have a signal necessary for an address signal.
In order to apply the cyanine dye solution to the substrate, it is preferable to use a spin coat method.
The light interference layer in the present invention may contain other compounds such as a singlet oxygen quencher, a light absorber, and a radical scavenger (scavenger) other than the above metal complex.
[0051]
A reflection layer may be provided in addition to the light interference layer, and a protective layer may be provided on the reflection layer, and further a protective layer may be provided on the substrate surface (laser light incident side).
Reflective layer has high reflectivity such as Au, Al, Ag, Cu, Pt formed by vapor deposition, sputtering, etc., each of these other alloys, and metal films such as alloys to which trace components other than these are added. Examples of the protective layer include a coating of a radiation curable resin such as an ultraviolet curable resin by a spin coating method for the purpose of protecting the optical information recording medium and improving weather resistance, and curing the radiation. An application layer is mentioned.
[0052]
In this way, an optical disc in which a light interference layer including a dye layer and a reflective layer are provided on a substrate, and further a protective layer is provided can be obtained. An optical disk having another similar configuration or another configuration having at least the optical interference layer may be bonded, or the substrates themselves may be bonded to face each other.
Materials and methods for this bonding include UV curable resins, cationic curable resins, double-sided PSA sheets, hot melt methods, spin coating methods, dispensing methods (extrusion methods), screen printing methods, roll coating methods, etc. It is done.
[0053]
DETAILED DESCRIPTION OF THE INVENTION
Details will be described in the following examples. A polycarbonate substrate having a track pitch length of 0.74 μm (or 0.80 μm) and having only a wobble signal (may also have a prepit signal) is used. (1) The recording layer is a compound belonging to the above general formulas [Chemical Formula 11] and [Chemical Formula 12], wherein n is 1 or 2, M is Fe, R₁, R₂Is a compound having the same or different lower alkyl group (an alkyl group having 5 or less carbon atoms (at least 5 carbon atoms), the same shall apply hereinafter), and (2) a compound belonging to the above general formula [Chemical Formula 13], wherein n is 1 Or 2, m and m ′ are the same or different from 1 to 5, and C_mH_2m  , C_{m '}H_{2m '}Are the same or different lower alkylene groups, or C_mH_2m  , C_{m '}H_{2m '}Any one of the compounds is a compound in which the terminal ferrocene group is a lower alkyl group which is a hydrogen atom, (3) a compound belonging to the above general formula [Chem. 14], wherein n is 1 or 2,₇, R₈Is a hydrogen atom and R_Five, R₆Are the same or different lower alkyl groups, m and m 'are 5 or less (at least 5) and are the same or different, and C_mH_2m  , C_{m '}H_{2m '}Are the same or different lower alkylene groups, or C_mH_2m  , C_{m '}H_{2m '}Any one of the compounds is a lower alkyl group in which the terminal ferrocene group is a hydrogen atom, and the N substituent other than the ferrocene group has 2 to 8 carbon atoms, (4) in the general formula [Chemical Formula 10] C1 is an alicyclic group (6-membered ring, 5-membered ring, 3-membered ring, etc.), C2 is the same or different alicyclic group or dimethyl as C1, and the others are (a) the above ▲ The same compound (R as 1)₁-M₁, R₂-M₂Are R in the above general formulas [Chemical Formula 11] and [Chemical Formula 12], respectively.₁, R₂A1 and A2 are naphthalene rings, R_ThreeIs a hydrogen atom, R_FourIs a hydrogen atom or a ferrocene group, X^-Is PF₆ ^-Or an anionic component of the general formula [Chemical Formula 11]), (b) a compound similar to (2) above (R₁-M₁, R₂-M₂Is N in the above general formula [Chem. 13]⁺It corresponds to a substituent and an N substituent, and A1 and A2 are naphthalene rings, R_Three, R_FourIs a hydrogen atom), (c) a compound similar to (3) above (R₁-M₁, R₂-M₂Is N in the above general formula [Chem. 14]⁺It corresponds to a substituent and an N substituent, and A1 and A2 are naphthalene rings, R_Three, R_FourIs a hydrogen atom), and in these (1) to (4), X^-Is an anion component of the above general formula [Chem. 11], ClO_Four ^-, PF₆ ^-Or BF_Four ^-In the substituted cyanine compound, the solution of each compound (dye), the solution in which each compound and an aminium light stabilizer are added, and (5) the above general formula [Chemical Formula 38] and the general formula A compound of the above general formula [Chemical Formula 36] comprising a combination of the formula [Chemical Formula 41], among which (6)₁, D₂Where both are hydrogen, (7) R_Three, R_FourAre the same or different and are lower alkyl groups having 1 to 4 carbon atoms, and among them, (7) in particular X^-Is ClO_Four ^-, PF₆ ^-Or BF_Four ^-Each of the indolenin-based cyanine dyes (n is preferably matched with n of each of the compounds (1) to (4)) of each of these compounds (5) to (7) A dye solution occupying a ratio of 50 to 100% by weight of the whole dye is prepared from the dyes belonging to each of the above (1) to (4), and each of these solutions is used for spin coating. It forms so that a dry film thickness may be 50-150 nm.
After that, a reflective layer of Au or Al is formed by sputtering, a protective layer made of ultraviolet curable resin is formed thereon by spin coating, and a polycarbonate substrate is bonded by an adhesive layer made of ultraviolet curable resin by spin coating. A bonded optical disc is obtained.
The optical disk thus obtained is excellent in light resistance and, for example, when recording is performed by irradiating a laser beam of 660 nm to 680 nm, for example, a trimethine cyanine compound into which a spiro condensed ring belonging to the above general formula [Chemical Formula 10] is introduced. Is used, the characteristics such as sensitivity, modulation degree, jitter, etc. are improved, the compound belonging to the above general formula [Chemical Formula 10] is not used, and instead, the trimethine represented by the above general formula [Chemical Formula 36] is used. The recording power can be further reduced as compared with an optical disk obtained in the same manner except that a cyanine compound is used.
The above uses a trimethine cyanine compound into which a spiro-fused ring is introduced, but in the case of CD-R use, the pentamethine-based cyanine compound into which a spiro-fused ring belonging to the above general formula [Chemical Formula 10] is introduced is also in accordance with the above. Can be used and results similar to the above can be obtained.
[0054]
【Example】
Next, examples of the present invention will be described.
Example 1
A transparent substrate made of polycarbonate having a thickness of 1.2 mm and an outer diameter (diameter) of 120 mm with a spiral groove having a width of 0.5 μm, a depth of 200 nm and a pitch of 1.6 μm formed on the surface was molded by an injection molding method. .
Next, 0.3 g of the pentamethine substituted cyanine compound of the following [Chemical Formula 48] is dissolved in 10 ml of diacetone alcohol, and the solution is applied to the surface of the substrate by spin coating (rotation speed: 2000 rpm) to form a film. A light interference layer composed of a photosensitive recording layer having a thickness of 70 nm was formed.
[0055]
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[0056]
With respect to this optical interference layer, an absorption spectrum [wavelength dependence in a wavelength range of 400 to 800 nm of absorbance (Abs)] measured by a visible ultraviolet spectrophotometer / U-4000 (manufactured by Hitachi, Ltd.) is shown in FIG. An absorption spectrum (change of absorption intensity (Absorbance) with respect to wavelength (Wavelength) (nm)) was obtained.
On this optical interference layer, an Ag film having a film thickness of 100 nm was formed by sputtering to form a reflective layer.
Further, an ultraviolet curable resin SD-211 (manufactured by Dainippon Ink & Chemicals, Inc.) was spin coated on the reflective layer, and the coating film was cured by irradiating with ultraviolet rays to form a protective film having a thickness of 5 μm.
[0057]
Recording was performed on the optical disk thus produced at a linear velocity of 19.2 m / sec using a DDU-1000 (Pulstec recorder) with NA (numerical aperture) = 0.53 and laser wavelength = 780 nm. As a result, the laser power was 26 mW (recording sensitivity, hereinafter the same). Thereafter, the apparatus was used to reproduce a signal with a laser output of 0.7 mW, and the reflectance, modulation factor, error rate, and jitter were measured. As a result, all showed good values.
Further, when the light resistance test was conducted using a xenon lamp, it was good.
[0058]
Comparative Example 1
In Example 1 above, instead of the compound of [Chemical Formula 48], N⁺Substituents and N-substituents are the same kind of methyl group (CH_ThreeAn optical disk was prepared in the same manner except that the compound (a1) was further used, and the compound (b1) in which the spiro-fused ring was a dimethyl group was used, and measured in the same manner as in Example 1. It was 25.5 mW and 28 mW. Thereafter, the apparatus was used to reproduce a signal with a laser output of 0.7 mW, and the reflectance, modulation factor, error rate, and jitter were measured. As a result, all showed good values.
Further, when the light resistance test was conducted in the same manner as in Example 1, none of the compounds using the compound (a1) and the compound (b1) reached a sufficient level.
In addition, when the absorption spectrum was measured about the optical interference layer similarly to Example 1, in the case of the compound (a1), the absorption spectrum shown in FIG. 2 was obtained in the case of the compound (b1).
[0059]
Example 2
A transparent substrate made of polycarbonate having a thickness of 1.2 mm and an outer diameter (diameter) of 120 mmφ having a spiral groove having a width of 0.32 μm, a depth of 100 nm and a pitch of 0.74 μm formed on the surface was molded by an injection molding method. .
In the same manner as in Example 1, except that this substrate was used, and a trimethine-based substituted cyanine compound of the following [Chemical Formula 49] was used instead of the compound of the [Chemical Formula 48], the optical interference was similarly performed. An ultraviolet curable resin SD-318 (manufactured by Dainippon Ink & Chemicals, Inc.) was dropped on the protective film of the substrate and the light interference layer on which the protective film was not formed. After that, another substrate (same material and dimensions) formed in the same manner as described above is placed thereon, and the resin is uniformly diffused by spin coating in the gap, and then irradiated again from the side of the substrate on which ultraviolet rays are superimposed. After curing, an adhesive layer having a thickness of 25 μm made of resin was formed in a region of 32 mmφ to 120 mmφ of the substrate from the beginning, and the stacked substrates were bonded together to produce a bonded optical disk.
Recording was performed on the optical disk thus produced at a linear velocity of 3.5 m / sec using a DDU-1000 (Pulstec recorder) with NA (numerical aperture) = 0.65 and laser wavelength = 660 nm. As a result, the laser power was 7.0 mW (recording sensitivity, the same applies hereinafter). Thereafter, the apparatus was used to reproduce a signal with a laser output of 0.7 mW, and the reflectance, modulation factor, error rate, and jitter were measured. As a result, all showed good values.
Moreover, it was favorable when the light resistance test was done similarly to the said Example 1.
In addition, when the absorption spectrum was measured about the optical interference layer similarly to Example 1, the absorption spectrum shown in FIG. 4 was obtained.
[0060]
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[0061]
Comparative Example 2
In Example 2 above, instead of the compound of [Chemical Formula 49], N⁺Substituent and N substituent are each methyl group (CH_Three) And butyl group (C_FourH₉And a bonded optical disk was prepared in the same manner except that the compound (b2) having a dimethyl group in the spiro-fused ring was used and measured in the same manner as in Example 1. The laser power was 11 mW. . Thereafter, the apparatus was used to reproduce a signal with a laser output of 0.7 mW, and the reflectance, modulation factor, error rate, and jitter were measured. As a result, all showed good values.
Moreover, when the light resistance test was done similarly to the said Example 1, compared with the thing of Example 2, it was inferior.
In addition, when the absorption spectrum was measured about the optical interference layer similarly to Example 1, the absorption spectrum (wave line) shown in FIG. 5 was obtained. In the figure, the solid line is in an acetone solution.
[0062]
【The invention's effect】
  According to the present invention,Since a substituted cyanine compound in which a spiro fused ring represented by the above general formula [Chemical Formula 10] is introduced and a substituent having a substituent of a metallocene compound is introduced into N of the heterocyclic ring is used,It can prevent light deterioration during long-term storage and playback with a large number of repetitions, and it does not impair recording and playback performance.Cyanine compoundsTo reduce the light absorption energy itself and prevent its degradation, and may not add stabilizing radicals, quenchers or other light stabilizers,Introducing a spiro fused ringTherefore, it has good reactivity with laser light selected from a wavelength range of around 350 nm to 830 nm,For example, thermal decomposition becomes high,An optical information recording medium having good recording sensitivity and capable of performing high-speed recording can be provided.
  In addition, it has good solubility in solvents and good film formability.Cyanine dyeAn optical information recording medium can be provided.
  Then, it is possible to provide an optical information recording medium to which the conventional manufacturing method of CD-R and DVD-R can be applied almost without major changes.
[Brief description of the drawings]
FIG. 1 is a diagram showing an absorption spectrum of a light interference layer composed of a dye layer containing a dye of one example (compound of the above [Chemical Formula 48]) belonging to the above general formula [Chemical Formula 10] according to the present invention.
FIG. 2 is a graph showing an absorption spectrum of a light interference layer composed of a dye layer containing one dye of the compound of the comparative example.
FIG. 3 is a graph showing an absorption spectrum of a light interference layer composed of a dye layer containing a dye of another example of the compound of the comparative example.
FIG. 4 is a diagram showing an absorption spectrum of an optical interference layer comprising a dye layer containing a dye of another example (compound of the above [Chemical Formula 49]) belonging to the above general formula [Chemical Formula 10] according to the present invention. .
FIG. 5 is a diagram showing an absorption spectrum of a light interference layer composed of a dye layer containing another example of the compound of the comparative example.

Claims (7)

In an optical information recording medium having a light interference layer including a recording layer on a substrate, the recording layer introduces a spiro-condensed ring into a cyanine compound represented by the following general formula [Chem. An optical information recording medium comprising a substituted cyanine compound into which a substituent having a substituent of a metallocene compound is introduced.
(However, N ⁺ X ^- represents the same as the N-X in a different notation, C1, C2 are both or either one represents a spiro fused ring, when either one thereof represents a spiro fused ring The other represents dimethyl, and X ⁻ represents a halogen atom, PF ₆ ⁻ , perchloric acid, borohydrofluoric acid, phosphoric acid, benzenesulfonic acid, SbF ₆ ⁻ , toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid. acid, trifluoromethyl carboxylic acid, periodic acid, SCN ^-, anions of tetraphenylborate and tungstate, and among the group of the dithiol complexing, anion obtained by metal complexes such as metallocene compound anion of represents an anion selected from, M _1, M ₂ represents a substituent group or a hydrogen atom of the metallocene _{compound, R 1 -M 1, R 2} -M 2 is small At least one of them may have another substituent substituted with a substituent of the metallocene compound, or a substituted or non-substituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl. Group, halogenated alkyl group, alkyl hydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkyl A sulfonyl group, an alkyl carboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl group and a phenoxyalkyl group (the hydrogen atom of the benzene ring portion and / or the alkyl portion is And may be substituted with a substituent other than a metal ion such as a ruthenium group, a carboxyl group, a hydroxyl group, or a halogen atom, and the same applies to the corresponding portion of the phenyl group, benzyl group, and alkylphenyl group. When both have a substituent substituted with a substituent of a metallocene compound, they may be the same or different, and only one of them has a substituent substituted with a substituent of a metallocene compound The other is a substituted or unsubstituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, halogenated alkyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkyl other than the substituent of the metallocene compound. Amido group, alkylamino group, alkylsulfonamido group, alkylcarbamoyl Group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkylsulfonyl group, metal carboxyl or alkylsulfonyl group bonded to alkyl group, phenyl group, benzyl group, alkylphenyl group and phenoxyalkyl group (The hydrogen atom of the benzene ring portion and / or the alkyl portion may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom, and the corresponding phenyl group, benzyl group, and alkylphenyl group) The same applies to the part. ) Represents a substituent selected from the group consisting of R ₃ and R ₄ are both hydrogen atoms, both or one of them is a substituent having a metallocene-based compound substituent, and both are the same However, in any one of them, the other represents a hydrogen atom or an organic substituent other than a substituent having a substituent of a metallocene compound, and R ₃ and R ₄ are a hydrogen atom or a metallocene group, respectively. A plurality of the same or different substituents selected from organic substituents other than the substituents having the substituents of the compound and the substituents having the substituents of the metallocene compound (any position where substitution is possible) may be used, and A1, A2 represents a substituted or unsubstituted benzene ring or naphthalene ring, n in the polymethine chain of the central linking chain represents a positive integer including 0, and the polymethine chain has a substituent. Alternatively, it may have a cyclic side chain extending between a plurality of carbons. )   The optical information recording medium according to claim 1, wherein the molecular weight of the substituent having a substituent of the metallocene compound is smaller than the molecular weight of the cyanine compound. The optical information recording medium according to claim _1, wherein R ₁ and R ₂ are C _n H _2n , n is 0 to 8, and may be the same or different. Wherein X ^- ClO ₄ ^-, PF ₆ ^- or BF ₄ ^- optical information recording medium according to any one of claims 1 to 3. 5. The optical information recording medium according to claim 1, wherein the metallocene compound is a compound represented by the following general formula [Chemical Formula 15].
(M represents a metal atom, and R ¹ and R ² represent a substituent.) M is Fe, Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr, Lu, W, Os or Ir, and R ¹ and R ² are hydrogen atoms and alkyl having 1 to 10 carbon atoms. Group or an alkyl halide group thereof, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aroyl group having 7 to 10 carbon atoms, an aldehyde group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Alkoxy group, C2-C10 amino group, hydroxyl group, halogen atom, boric acid group, benzoyl group, C2-C10 alkeni group including lower alkenyl group, hydroxyalkyl group, acetyl group, aliphatic cyclic group Alternatively, the optical information recording medium according to claim 5, which represents an alkoxycarbonyl group (each may have a substituent) and may be the same or different. 7. The optical information recording medium according to claim 1, wherein at least one of R ₁ -M ₁ and R ₂ -M ₂ has a branched side chain .