HK1024330B - Optical information recording medium - Google Patents

Description

Optical information recording medium

The present invention relates to a rewritable optical information recording medium of a thermal mode capable of recording and reproducing by a laser beam of a short wavelength region such as DVD-R.

Means for recording and reproducing data such as images, and sounds of characters, graphics, and the like are known as recording materials for recording and reproducing data by using laser light having a wavelength of 770 to 830nm, for example, a CD-R (compact disc-read) having a recording layer containing pentamethyl cyanine, but DVD-R (Digital, video, Digital versatile disc-read) capable of high-density recording and reproducing data by using red laser light having a shorter wavelength of, for example, 620 to 690nm has been used as a medium.

As such a DVD-R, an optical information recording medium having a recording layer using a specific trimethy cyanine dye is disclosed in Japanese patent application No. 9-251487.

However, in the above-described description, when the substituent of the benzene ring or the naphthalene ring of the trimethine cyanine dye having a benzene ring or a naphthalene ring bonded to the indole ring is a hydrogen atom or the like not including a nitro group, the absorption spectrum of the optical interference layer having the dye layer containing the dye is shown in FIG. 1, and the absorbance h is the absorbance at the sub-peak b of the absorption due to the interaction and association between the dye molecules₂Formation of color with respect to absorption due to band gap energy of dye moleculeAbsorbance h of the main peak a of absorption of the element molecule itself₁Since the spectrum composed of the main peak a and the sub peak b is too large, the spectrum does not have a sharp shape, and the half-value width d of the spectrum showing the sharp shape (the width of the spectrum composed of the main peak a and the sub peak b with respect to the absorbance of h 1/2) cannot be reduced.

As described above, when the spectrum cannot be formed into a sharp shape, the recording sensitivity when the optical interference layer is irradiated with laser light to form grooves, that is, the absorbance per unit film thickness of the optical interference layer cannot be increased, so that it is necessary to increase the thickness of the pigment layer, increase the recording power, or decrease the recording speed, and also to influence the modulation degree, vibration (Jitter), and other characteristics because the grooves are easily deformed by heat accumulation that is likely to occur between the grooves and the grooves during recording, so-called thermal interference is likely to occur.

The 1 st object of the present invention is to provide an optical information recording medium having an optical interference layer which can improve the ratio of the absorption peak of dye molecules to the association peak of the dye molecules associated with the dye molecules by using a short-wavelength laser beam for recording on DVD.

The 2 nd object of the present invention is to provide an optical information recording medium which can obtain an optical interference layer having a small film thickness and excellent recording sensitivity with respect to a short wavelength laser beam of a DVD.

The 3 rd object of the present invention is to provide an optical information recording medium having excellent characteristics such as a modulation factor and vibration with respect to a short wavelength laser beam for recording on a DVD.

The 4 th object of the present invention is to provide an optical information recording medium which has a low recording power and can record at a high speed with respect to a short wavelength laser beam for recording on a DVD.

The present inventors have conducted extensive studies to solve the above problems and found that an optical interference layer of a trimethylsilyl cyanine pigment having a substituent having a nitro group on a benzene ring bonded to an indole ring or a naphthalene ring in a pigment layer, particularly for a short-wavelength laser beam for recording on a DVD, has a lower minor peak to major peak and can sharpen a spectrum composed of the major peak and minor peaks as shown in FIG. 1, thereby completing the present invention.

Accordingly, the present invention provides an optical information recording medium (1) comprising an optical interference layer containing a dye layer on a substrate, wherein the dye layer contains a trimethine-based cyanine dye represented by the following general formula [ formula 1], and the optical interference layer can be recorded and reproduced by a laser beam having a wavelength selected from the range of 620nm to 690 nm.

[ claim 1]

[ however, A represents the following general formula [ formula 2]][ chemical formula 5]]Any one of (1), (2)[ CHEM 3][ CHEM 4][ CHEM 5]A' represents the following general formula [ formula 6]][ chemical formula 9]]Any one of (1), (chemical) 6[ CHEM 7 ][ CHEM 8 ][ CHEM 9]

A and A 'may be the same or different (except that M, n are the number of substituents, each being 1 or a plural integer), R, R' represent a group selected from a substituted or unsubstituted alkyl group, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, an alkoxy group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkylamido group, an alkylamino group, an alkylsulfonamido group, an alkylcarbamoyl group, an alkylaminosulfonyl group, a hydroxyl group, a halogen atom, an alkylalkoxy group, a halogenated alkyl group, an alkylsulfonyl group, an alkylcarboxyl group bonded to a metal ion or an alkyl groupOr substituents of the group consisting of alkylsulfonyl, phenyl, benzyl, alkylphenyl and phenoxyalkyl (the hydrogen atom of the benzene ring moiety and/or the alkyl moiety may be substituted with a substituent other than the metal ion such as alkyl, carboxyl, hydroxyl or halogen atom, and the same may be said for the above-mentioned phenyl, benzyl and alkylphenyl moieties), which may be the same or different, X^-Is selected from halogen atoms, PF₆ ^-，SbF₄ ^-Phosphoric acid, perchloric acid, borohydridof acid, benzenesulfonic acid, toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-Anions of the anion groups of tetraphenylboronic and tungstic acids]

The present invention also provides (2) the optical information recording medium of the above (1), wherein the dye layer contains a dye other than the trimethine cyanine dye of the above general formula [ 1], and the total dye contains at least 50% by weight of the trimethine cyanine dye of the above general formula [ 1 ]. (3) There is provided the optical information recording medium as described in the above (1) or (2), wherein the optical interference layer contains a metal complex.

The optical interference layer of the present invention can be recorded and reproduced by a laser beam having a wavelength in the range of 620nm to 690nm, and can be used for DVD-R.

The optical interference layer of the present invention is composed of a pigment layer composed of an organic pigment material, a layer composed of another organic material or an inorganic material, and includes a recording layer containing a single layer or a plurality of pigment layers capable of forming grooves by laser irradiation; a reinforcing layer made of, for example, a resin material, having a refractive index and a film thickness adjusted for the purpose of adjusting the optical properties of the optical information recording medium, in addition to the recording layer; further, an intermediate layer or the like is provided between the substrate and the pigment layer, when the pigment layer is a multilayer. The optical interference layer is a general term for these recording layers and the like.

The pigment layer contains the above general formula (formula 1)]Represents a trimethylsilyl cyanine dye, and examples of the dye include those wherein A is an optionally selected group from the general formula [ formula 2]][ chemical formula 5]]In the general formula, A' is optionally selected from the aboveGeneral formula [ chemical 6]][ chemical formula 9]]The general formula (I) and the two compounds are selected and combined respectively. For example, general formula [ chemical 2]]And general formula [ chemical 6]][ chemical formula 9]]Each combination of them, other general formula [ 3]][ chemical formula 5]]The same applies. Substituents of A, A' (NO)₂)m，(NO₂) n is at least 1, and the plural integer is an integer of 2 or more. These pigments may be used alone or in combination.

When a light interference layer containing a trifluoromethyl cyanine dye (having a nitro substituent on a benzene ring or a naphthalene ring bonded to an indole ring) is irradiated with laser light, the ratio h of the absorbance of a main wave A to that of a sub wave b can be adjusted when the spectrum of the absorbance at the wavelength of the laser light is represented by the symbol in FIG. 1₂/h₁Is less than 0.8, and the half-value width d of the spectrum composed of the main peak A and the sub-peak b is less than 100 nm. Substitution of the above general formula [ formula 1] with other substituent such as hydrogen atom]In the case of nitro group as a substituent of A, A', the above absorbance ratio h₂/h₁At least 0.8 or more and not reduced to 0.8 or less, and the half width d of the spectrum is at least 100nm or more and not reduced to 100nm or less.

As described above, introduction of a nitro group into the benzene ring or naphthalene ring bonded to the indole ring of the trifluoromethyl cyanine dye reduces the secondary peak, sharpens the spectrum (Sharp) composed of the main peak and the secondary peak, increases the absorbance per unit film thickness of the optical interference layer, and improves the recording efficiency, in other words, the recording sensitivity. When the recording sensitivity is improved, even if the film thickness of the optical interference layer is thinner than the conventional one, for example, at most 70nm, that is, 70nm or less, the modulation degree can be made to conform to the current specification, and the heat accumulation between grooves at the time of recording can be suppressed because the film thickness is thin, so-called thermal interference phenomenon, which is deformation of the grooves due to the heat accumulation, can be suppressed, and the vibration characteristics are good.

When the recording sensitivity is good and the characteristics such as the modulation degree and the vibration are good, the recording power can be reduced or the recording speed can be increased.

The optical interference layer of the present invention may be provided with the same dye layer or another dye layer in which one or more kinds of other dyes other than the above-mentioned tridymite of the general formula [ 1] are used, and when the tridymite of the general formula [ 1] is mixed in the total dye by at least 50 wt%, that is, when a mixed system in which 50 wt% or more of the above-mentioned is mixed is formed, the modulation degree or vibration characteristics are slightly inferior to those when the above-mentioned other dyes are not mixed, but the above-mentioned specifications are satisfied.

Examples of the other pigments include a tertiary methyl cyanine pigment represented by the following general formula [ formula 10 ].

[ solution 10)]

[ however, B represents the following general formula [ 11]][ chemical formula 14 ]]Any one of them][ CHEM 11][ CHEM 12 ][ CHEM 13 ][ CHEM 14 ]B' represents the following general formula [ formula 15 ]]18 of- [ - ] transformation]Any of (1), (CHEM 15)[ CHEM 16 ][ CHEM 17 ][ CHEM 18 ]

B and B' may be the same or different (except that D₁，D₂Are independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkylamido group, an alkylamino group, an alkylsulfonamido group, an alkylcarbamoyl group, an alkylaminesulfonyl group, an alkylsulfonyl group, a phenyl group, a cyano group, an ester group, a nitro group, an acyl group, an allyl group, an aryl group, an aryloxy group, anSubstituents selected from the group consisting of thio, phenylazo, pyridylazo, alkylcarbonylamino, sulfonamido, amino, alkylsulfo, thiocyano, mercapto, chlorosulfonyl, alkylazochromyl, alkylaminosulfonyl, vinyl and sulfo, which may be the same or different, and p and q are the number of substituents and each represents 1 or more integers (excluding D)₁，D₂While only nitro groups are selected)). R, R' are the same as the above general formula [ formula 1]]Are identical to each other]。

This general formula [ chemical 10]]Wherein B is any selected from the above general formula [ formula 11]][ chemical formula 14 ]]Wherein B' is any one selected from the general formula [ formula 15 ]]18 of- [ - ] transformation]One of them, and both of them are selected to be respectively all combined compounds. For example, there is a general formula of formula [ chemical formula 11]]And general formula [ Hua 15 ]]18 of- [ - ] transformation]Each combination of them, and the other general formula [ 12 ]][ chemical formula 14 ]]The same applies. Substituents (D) of B, B₁)p，(D₂) q is at least 1, and a plurality of integers, i.e., integers of 2 or more.

The synthesis of the dye represented by the general formulae [ formula 1] and [ formula 11] can be carried out by the method described in the chemistry of Synthetic Dyes Vol 14.

The above-mentioned trimethine cyanine dye of the general formula [ 1] or other dyes may be used alone, but in order to improve light resistance, a metal complex compound as a light stabilizer may be contained in the dye layer or other layers.

Such a metal complex compound has, for example, the following general formula [ formula 19]]The compounds represented by the formula (I). [ CHEM 19]

[ wherein R¹，R²Are each represented by SO₂R³(however, R is not limited thereto³Is as follows [ chemical formula 20]]Representation), [ chemical 20]Halogen atom, phenyl group, alkyl group, cyano group, sulfurized alkyl group, alkylsulfonyl group, R, s is an integer of 1 to 4, R is⁴Is alkyl, Y represents N or P, M represents Cu, Co or NiA metal thereof.

The above general formula [ CHEM 19]]The specific compound of (b) is, for example, the following chemical formula 21 in addition to those shown in the examples described below][ solution 22 ]]The compound of (1). [ CHEM 21 ][ CHEM 22 ]

Brief description of the drawings

FIG. 1 is an absorption spectrum diagram of an optical interference layer of the present invention comprising a dye layer containing a tertiarymethyl cyanine dye of formula [ 1] or less (a dye of formula [ 10 ]).

FIG. 2 is an absorption spectrum diagram of an optical interference layer of the present invention comprising a dye layer containing a dye belonging to one example of the above general formula 1.

FIG. 3 is an absorption spectrum diagram of an optical interference layer of the present invention comprising a dye layer containing a dye belonging to another example of the above general formula 1.

FIG. 4 is an absorption spectrum diagram of an optical interference layer of the present invention composed of a dye layer composed of a dye of formula 1 and a dye of formula 10.

FIG. 5 is an absorption spectrum diagram of an optical interference layer composed of a dye layer containing an azo dye.

In the production of the optical information recording medium of the present invention, the cyanine dye represented by the general formula [ chemical formula 1], or a mixed dye in which these dyes are dissolved with other dyes of the cyanine dye represented by the general formula [ chemical formula 10] (preferably, the former is mixed in an amount of 50 wt% or more), or the metal complex represented by the general formula [ chemical formula 19] is dissolved in a solution of the dyes, and then the solution is applied onto a light-transmitting substrate. As the dye solution, fluorine-based solvents such as chloroform, dichloroethane and fluorinated alcohol, cellosolves such as methyl ethyl ketone, dimethylformamide, methanol, toluene, cyclohexanone, acetylacetone, diacetone alcohol and methyl cellosolve, dioxane and the like can be used. In this case, the mixing ratio of the cyanine dye is preferably 1 to 10 wt%.

The substrate used in the present invention is, for example, glass or plastic such as epoxy resin, methacrylic resin, polycarbonate resin, polyester resin, polyvinyl chloride resin, polyolefin resin, etc. The substrate can be formed with track grooves or grooves, or can be provided with signals required by address signals.

The cyanine dye solution is preferably applied to a substrate by spin coating. The thickness of the coating layer after drying can be the same as that used in the prior art.

The optical interference layer of the present invention may contain other compounds than the above-mentioned metal complex compounds, such as singlet oxygen scavengers, light absorbers, and radical scavengers.

A reflective layer may be provided in addition to the optical interference layer, and the reflective layer may have a protective layer thereon, and further, may have a protective layer on the substrate surface (the laser light incident side).

Examples of the reflective layer include a high-reflectance material film such as a metal film of Au, Al, Ag, Cu, Pt, other alloys thereof, alloys containing a trace amount of these other elements, and the like formed by vapor deposition, sputtering, and the like, and examples of the protective layer include a coating layer which is cured by radiation by applying a solution of a radiation-curable resin such as an ultraviolet-curable resin by a spin coating method or the like so as to protect an optical information recording medium and improve weather resistance.

Thus, an optical disk can be obtained in which an optical interference layer containing a pigment layer, a reflective layer, a protective layer, and the like are provided on a substrate. The optical disks of the same or different structures including at least the optical interference layer may be bonded together, or the substrates may be bonded together.

As the material for bonding, for example, an ultraviolet curable resin, a cationic curable resin, a double-sided adhesive sheet, a hot-melt method, a spin coating method, a dispersion method (extrusion method), a screen printing method, a roll coating method and the like can be used.

According to the following embodiments, a polycarbonate substrate having a track pitch of 0.74 μm (or 0.80 μm) and a wobble signal only (or a pre-groove signal at the same time) is used, and the pigment layer of the optical interference layer is represented by the general formula [ formula 1]]Of the compound of formula (2)]And general formula [ chemical 6]]A pigment formed by the combination of (A) and (B), especially a pigment in which m and n are both 1; (iii) pigments having R and R' as the same and having C8 as the center and an unbranched alkyl group or a phenylalkyl (lower alkyl) group, and (iv) a tri-methine cyanine pigment of the indolenine (インドレニン) series, particularly, a pigment wherein X-is an anion of perchloric acid, and a solution of each pigment, each pigment belonging to (i) to (iv) and each pigment belonging to the above general formula (19)]And R is³To [ dissolve in 20]]The solution of the metal complex, and the pigment solution further added with a dye of the above general formula [ formula 10]]Of the compound (v) represented by the general formula (11)]And general formula [ chemical 16 ]]The pigment, especially D, formed by the combination of₁，D₂The pigment, R are hydrogen atoms at the same time²A dye having a lower alkyl group of 3, 4 or the like; especially, each indolenine pigment of the pigment of which X-is an anion of iodine, and a solution of each pigment belonging to the above-mentioned fifth to the above-mentioned eighth groups is prepared. The pigment solutions of the above-mentioned (I) to (IV) account for 60 to 70 parts by weight of the total pigment. The dye layer of the optical interference layer having a dry film thickness of 50 to 70nm can be formed by spin coating using these solutions. The absorption spectrum of the optical interference layer shows the absorbance ratio h of the absorption peak shown in FIG. 1₂/h₁At the highest, 0.8, in other words, 0.8 or less, preferably 0.6 to 0.75, and the half width d of the spectrum composed of the main peak a and the sub-peak b is 100nm or less, preferably 80 to 100 nm. Then, a reflective layer of Au or Al is provided by sputtering, and an ultraviolet-curing resin is formed thereon by spin coatingThe protective layer is further bonded to a polycarbonate substrate by an adhesive agent composed of an ultraviolet curable resin by spin coating to obtain a bonded optical disc.

When the optical disk obtained as described above is irradiated with a laser beam of 620 to 690nm to record, the characteristics such as modulation and vibration can be improved, and the recording power can be reduced or the recording speed can be improved even when the recording power is the same as that of the optical disk obtained by replacing the pigments belonging to the first to fifth of the general formula 1 with the pigments belonging to the fifth of the general formula 1.

[ examples ]

Example 1

A transparent substrate made of polycarbonate having a thickness of 0.6mm and an outer diameter (diameter) of 120mm phi and having a spiral group with a width of 0.32 mu M, a depth of 100nm and a pitch of 0.74 mu M on the surface is formed by injection molding.

Then, the following chemical formula 23 was mixed at a weight ratio of 95: 5]Shown is a tertiary methyl cyanine NK-2084 (manufactured by Nippon phytochrome research Co., Ltd.) and represented by the following formula [ formula 24]]The light stabilizer of the metal complex is obtained by dissolving the mixture in a fluorinated alcohol such as 2, 2, 3, 3-tetrafluoro-1-propanol (TFP, manufactured by Tokyo chemical Co., Ltd.) to 3% by weight, and spin-coating the solution on the surface of a substrate to form a light interference layer composed of a photosensitive pigment film having a film thickness of 60 nm. [ CHEM 23 ][ CHEM 24]

The wavelength dependence of the absorption spectrum [ absorbance (AbS) wavelength of 400-800 nm ] of the optical interference layer is measured by a visible ultraviolet spectrophotometer/U-4000 (manufactured by Hitachi, Ltd.)]The spectrum as shown in FIG. 2 was obtained. The ratio of absorbance of the minor peak to the major peak (to the absorbance h in FIG. 1)₂/h₁Corresponding) is 0.74, the half-value width of the spectrum (corresponding to the spectrum consisting of the main peak and the sub-peak vs. h of FIG. 1)₁/h₂The width d corresponds to)96nm。

An AU film having a thickness of 80nm is formed on the optical interference layer from the entire region of 44mm phi to 117mm phi of the substrate by sputtering, and a reflective layer is formed.

An ultraviolet-curing resin SD-211 (manufactured by Dainippon ink chemical industries, Ltd.) was spin-coated on the reflective layer, and the coating was cured by irradiating ultraviolet rays to form a protective film having a thickness of 5 μ M.

Further, an ultraviolet-curing resin SD-318 (manufactured by Dainippon ink chemical industries Co., Ltd.) was dropped on the protective film of the substrate and the optical interference layer on which the protective film was not formed, and then another substrate formed by the same method was placed thereon, and after the resin was spread to the gap by a spin coating method, the substrate side was irradiated with ultraviolet rays to cure the resin, and an adhesive layer having a thickness of 25 μ M and made of the resin was formed in the region of 32mm phi to 120mm phi of the substrate, and the stacked substrates were bonded to each other to produce a bonded type optical disk.

According to the Specification of DVD Specification for Read-only Disc, a DDU-1000(pulse recorder) with NA (numerical aperture) of 0.6 laser wavelength of 635nm is recorded on the above-mentioned manufactured optical Disc at a linear speed of 3.5M/sec, and then vibration is measured by time interval analyzer/TA-320 manufactured by Yokogawa electric company, the Data to clock Jitter is to normalize the offset sigma of the binary Data edge signal with the channel bit rate of 26.6mbps (38.23n SE c) as the reference clock, the evaluation reference for Jitter is to set the minimum groove length to 0.4 μm, when the EFM signal at the linear speed of 3.5M/s is modulated and normalized by the clock pulse, further, in order to prevent the signal from being modulated inversely by an error, it is preferable that 9% be the limit thereof, and 8.5% or less, in other words, not more than 8.5% at the highest.

And measuring the modulation I after recording by using a laser having a wavelength of 650nm₁₄/I_topI_topThe maximum reflected light quantity of the HF (EFM) signal is almost equal to I₁₄The maximum reflected light quantity is consistent. I is₁₄The light quantity sum of the diffracted light returned to the objective lens in the longest groove to be recorded in the recorded groupThe signal of the optical modulation component is formed by the difference of the light quantity reflected back to the lens at the non-groove portion.

A light resistance test of W.O.M. (Weather-meter) was conducted on the optical disk obtained as described above. The measurement conditions were such that Atolas weather-meterC 135A manufactured by Toyo Seiki Seisaku-Sho was used to irradiate a xenon light source with 6.5kw of light through the main surface of an optical disk for 80 hours at a temperature of 30 ℃ and a humidity of 70-80% RH to obtain the above-mentioned modulation factor (I) before and after the test₁₄/I_top) And compared.

The results of the above measurements are shown in Table l. The table shows the specification values that are now commonly used.

In this example, when using the above general formula [ formula 1], A and A 'are benzene rings having one nitro group and R' are the same alkyl group having 8 carbon atoms, a high modulation degree and also a low Jitter can be obtained by recording with a laser beam having a wavelength of 635nm and reproducing with a laser beam having a wavelength of 650 nm. The light resistance was good from the modulation degrees before and after the light resistance test. Example 2

An optical interference layer composed of a pigment layer was produced by the same method as in example 1 except that the above-mentioned trimethine cyanine pigment of formula [ 25] shown below of formula [ 1] was used in place of the trimethine cyanine pigment NK-2084 of example 1, and an optical disk was produced by the following steps, the results of measuring the optical interference layer by the same method as in example 1 are shown in FIG. 3 and Table 1, and the results of measuring the optical interference layer are shown in Table 1 by the same method as in example 1.

The optical disk of this embodiment has the same general formula as that of the pigment used in embodiment 1]Wherein R and R' are the same phenylethyl group, but recording by a laser beam having a wavelength of 635nm and reproduction by a laser beam having a wavelength of 650nm are possible, Jitter is not high, and the modulation degree is slightly better than that of example 1. [ CHEM 25]

Example 3

Except that the weight ratio is 6035: 5 Using the tertiarymethyl cyanine NK-2084 of example 1, the following formula was formulated as [ 26 ]]An optical interference layer composed of a pigment layer was formed in the same manner as in example 1 except for the tertiary methyl cyanine NK-4370 (manufactured by Nippon Photosensitve dyes research Co., Ltd.) and the metal complex, and the optical interference layer was measured in the same manner as in example 1, the results are shown in FIG. 4 and Table 1, and the optical disks were recorded in the same manner as in example 1, and the results are shown in Table 1. [ CHEM 26 ]

The optical disk of this embodiment uses an example in which the above-mentioned trimethine cyanine dye NK-2084 belonging to the above-mentioned formula [ CHEMICAL 1] and the above-mentioned trimethine cyanine dye NK-4370 belonging to the above-mentioned formula [ CHEMICAL 10] are mixed (weight ratio 60: 35), and can be reproduced by laser recording with a wavelength of 635nm with a laser of 650nm, which is higher than those of examples 1 and 2, and which has a poor modulation degree and cannot meet the specification value.

Example 4

Except for the above [ chemical formula 25] of practical example 2]The above-mentioned tertiary methyl cyanine and the compound (24) not used]The results of measuring the optical interference layer in the same manner as in example 1 (absorption spectrum of the optical interference layer, calculated value h based on the absorption spectrum, etc.) are shown in Table 1₂/h₁D is almost the same as that in FIG. 2), the optical disk was recorded in the same manner as in example 1, and the measurement results are shown in Table 1.

The optical disk of this example is an example not using a light stabilizer of a metal complex, and can be recorded by a laser beam having a wavelength of 635nm and reproduced by a laser beam having a wavelength of 650nm, and has a modulation degree lower than that of examples 1 and 2, but the result of the light resistance test is slightly inferior. Comparative example 1

An optical interference layer composed of a dye layer was produced in the same manner as in example 1 except that an azo dye (available from Altorich, Inc., type 36, 482, Disperse Red13) was used in place of the trimethylsilyl cyanine dye NK-2084 of example 1 and that the metal complex of formula [ 24] was not used, and an optical disk was produced by carrying out the procedures described below, and the results of measuring the optical interference layer in the same manner as in example 1 are shown in FIG. 5 and Table 1, and the results of measuring the optical interference layer in the same manner as in example 1 are shown in Table 1.

The optical disk of this comparative example uses an azo dye not belonging to the general formula [ 1] and not belonging to a cyanine dye, and does not use a metal complex as a light stabilizer, and the absorbance ratio of the sub peak/main peak, the half-value width of the spectrum composed of the main peak and the sub peak are both larger than those of the above examples, and the light resistance test result is also poor except for Jitter.

From the above results, it is found that the absorbance ratio and half-value width of the secondary peak/main peak are significantly different when the examples and the comparative examples are compared, and the absorption peak of the optical interference layer of the examples is sharper than that of the comparative examples, which can sufficiently reflect the Jitter characteristic. In the examples, when a metal complex is used in combination as a light stabilizer, light resistance is remarkably improved.

From these results, the present invention can limit the Jitter to 8.5 or less and the modulation degree to 70% or more (66% or more when used together with a dye not belonging to the general formula [ formula 1 ]), and the wavelength of the maximum absorption peak (main peak) and the wavelength of the second maximum absorption peak (sub peak) of the visible-ultraviolet spectrophotometer of the optical interference layer to 500 to 655 nm.

The present invention is limited to a part of various combinations of the general formula [ chemical formula 1], the general formula [ chemical formula 10], and the general formula [ chemical formula 19], or to a part or all of the dye or metal complex as described in the preferred embodiment, and further, the above-mentioned limitations can be added.

The present invention provides an optical information recording medium, which is characterized in that it is capable of providing an optical interference layer capable of improving the absorbance ratio of the main peak and the sub-peak of the dye by using a short wavelength laser for recording on DVD, and forming a sharp peak by reducing the half-value width of the spectrum constituted by these peaks, thereby achieving an optical interference layer having excellent recording sensitivity and a thinner film thickness, and having excellent characteristics such as modulation degree and Jitter, and low recording power, and capable of performing high-speed recording.

[ Table 1]

	Absorbance ratio of absorption peak (h in FIG. 1)2/h1Corresponding)	Half-value width (nm) of spectrum (corresponding to FIG. 1, d)	Jitter(％)	Degree of modulation I14/Itop(％)
						Before light resistance test	After light fastness test
				Specification value	-			-	Less than 9	Greater than 60	Greater than 60
Example 1	0.74	96	8.0			70	65
				Example 2	0.77			98	8.0	72	68
Example 3	0.79	99	8.5			66	62
				Example 4	0.77			98	8.0	74	20
Comparative example 1	0.97	130	15.0			70	15

Claims (20)

1. An optical information recording medium having an optical interference layer containing a dye layer on a substrate, characterized in that the dye layer contains a compound represented by the following general formula [ formula 1]]Indicating a trimethylsilyl cyanine dye, which can be recorded and reproduced by a laser beam having a wavelength selected from the range of 620nm to 690nm [ chemical formula 1]Wherein A represents the following general formula [ formula 2]][ chemical formula 5]]Any one of (1), (2)[ CHEM 3][ CHEM 4][ CHEM 5]A' represents the following general formula [ formula 6]][ chemical formula 9]]Any one of (1), (chemical) 6[ CHEM 7 ][ CHEM 8 ][ CHEM 9]

A and A 'may be the same or different (provided that m and n are the number of substituents and are each an integer of 1 or plural), R and R' may be the same or different and represent a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, an alkoxy group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkylamido group, an alkylamino group, an alkylsulfonamido group, an alkylcarbamoyl group, an alkylaminosulfonyl group, a hydroxyl group, a halogen atom, an alkylalkoxy group, a halogenated alkyl group, an alkylsulfonyl group, an alkylcarboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl groups and a phenoxyalkyl group (the hydrogen atom of the benzene ring moiety and/or the alkyl moiety may be substituted by a substituent other than a metal ion such as an alkyl group, carboxyl group, hydroxyl group, x^-Is selected from halogen atoms, PF₆ ^-，SbF₆ ^-Phosphoric acid, perchloric acid, borohydridof acid, benzenesulfonic acid, toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-Anions of the anion group of tetraphenylboronic and tungstic acids.

2. The optical information recording medium according to claim 1, wherein the dye layer contains a dye other than the trimethine cyanine dye of the general formula [ 1], and the total dye contains at least 50% by weight of the trimethine cyanine dye of the general formula [ 1 ].

3. The optical information recording medium according to claim 2, wherein the other dye is represented by the following general formula [ formula 10]]Represents a tertiary methyl cyanine dye of formula 10]Wherein B represents the following general formula 11][ chemical formula 14 ]]Any of (1), (CHEM 11)[ CHEM 12 ][ CHEM 13 ][ CHEM 14 ]B' represents the following general formula [ formula 15 ]]18 of- [ - ] transformation]Any of (1), (CHEM 15)[ CHEM 16 ][ CHEM 17 ][ CHEM 18 ]

B and B' may be the same or different, wherein D₁，D₂Are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkylamide group, an alkylamino group, an alkylsulfonamide group, an alkylcarbamoyl group, an alkylaminesulfonyl group, an alkylsulfonyl group, a phenyl group, a cyano group, an ester group, a nitro group, an acyl group, an allyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a phenylazo group, a pyridylazo group, an alkylcarbonylamino group, a sulfonamide group, an amino group, an alkylsulfo group, aThe substituents of the group, vinyl group and sulfo group, which may be the same or different, p, q are the number of substituents and each represent 1 or a plural integer (excluding D)₁，D₂In the case where only nitro groups are selected), R, R' are as defined above for the general formula [ formula 1]]The same is true.

4. The optical information recording medium of claim 1, wherein the optical interference layer contains a metal complex compound.

5. The optical information recording medium of claim 2, wherein the optical interference layer contains a metal complex compound.

6. The optical information recording medium of claim 3, wherein the optical interference layer contains a metal complex compound.

7. The optical information recording medium of claim 4, wherein the metal complex compound is represented by the following general formula [ formula 19]]Show, [ CHEM 19]Wherein R is¹，R²Are each represented by SO₂R³Wherein R is³Is as follows [ chemical formula 20]]The radical [ CHEM 20]Halogen atom, phenyl group, alkyl group, cyano group, sulfurized alkyl group, alkylsulfonyl group, R, s is an integer of 1 to 4, R is⁴Is an alkyl group, Y represents N or P, and M represents a metal such as Cu, Co or Ni.

8. The optical information recording medium of claim 6, wherein the metal complex compound is represented by the following general formula [ formula 19]]Show, [ CHEM 19]Wherein R is¹，R²Are each represented by SO₂R³Wherein R is³Is as follows [ chemical formula 20]]The radical [ CHEM 20]Halogen atom, phenyl group, alkyl group, cyano group, sulfurized alkyl group, alkylsulfonyl group, R, s is an integer of 1 to 4, R is⁴Is an alkyl group, Y represents N or P, and M represents a metal such as Cu, Co or Ni.

9. The optical information recording medium according to claim 1, wherein the wavelength of the maximum absorption peak (main peak) and the wavelength of the 2 nd maximum absorption peak (sub peak) of the optical interference layer measured by a visible ultraviolet spectrophotometer are 500 to 655 nm.

10. The optical information recording medium according to claim 3, wherein the wavelength of the maximum absorption peak (main peak) and the wavelength of the 2 nd maximum absorption peak (sub peak) of the optical interference layer measured by a visible ultraviolet spectrophotometer are 500 to 655 nm.

11. The optical information recording medium according to claim 7, wherein the wavelength of the maximum absorption peak (main peak) and the wavelength of the 2 nd maximum absorption peak (sub peak) of the optical interference layer measured by a visible ultraviolet spectrophotometer are 500 to 655 nm.

12. The optical information recording medium according to claim 8, wherein the wavelength of the maximum absorption peak (main peak) and the wavelength of the 2 nd maximum absorption peak (sub peak) of the optical interference layer measured by a visible ultraviolet spectrophotometer are 500 to 655 nm.

13. The optical information recording medium as claimed in claim 1, wherein the optical interference layer has a dominant peak h in an absorption spectrum measured with a visible ultraviolet spectrophotometer at a wavelength of 400 to 800nm₁And the sub-peak h₂The absorbance ratio h of₂/h₁Is 0.8 or less, and the half-value width of the spectrum composed of the main peak and the sub-peak is 100 nm.

14. The optical information recording medium according to claim 9, wherein the optical interference layer has a dominant peak h in an absorption spectrum measured with a visible ultraviolet spectrophotometer at a wavelength in the range of 400 to 800nm₁And the sub-peak h₂The absorbance ratio h of₂/h₁Is 0.8 or less, and the half-value width of the spectrum composed of the main peak and the sub-peak is 100 nm.

15. The optical information recording medium according to claim 10, wherein the optical interference layer has a dominant peak h in an absorption spectrum measured with a visible ultraviolet spectrophotometer at a wavelength in the range of 400 to 800nm₁And the sub-peak h₂The absorbance ratio h of₂/h₁Is 0.8 or less, and the half-value width of the spectrum composed of the main peak and the sub-peak is 100 nm.

16. The optical information recording medium according to claim 11, wherein the optical interference layer has a dominant peak h in an absorption spectrum measured by a visible ultraviolet spectrophotometer at a wavelength in the range of 400 to 800nm₁And the sub-peak h₂The absorbance ratio h of₂/h₁Is 0.8 or less, and the half-value width of the spectrum composed of the main peak and the sub-peak is 100 nm.

17. The optical information recording medium according to claim 12, wherein the optical interference layer has a dominant peak h in an absorption spectrum measured with a visible ultraviolet spectrophotometer at a wavelength in the range of 400 to 800nm₁And the sub-peak h₂The absorbance ratio h of₂/h₁Is 0.8 or less, and the half-value width of the spectrum composed of the main peak and the sub-peak is 100 nm.

18. The optical information recording medium according to claim 7, wherein A which is a compound of the general formula [ chemical formula 1] is a compound of the general formula [ chemical formula 2], A 'is a compound of the general formula [ chemical formula 6], m and 1, R, R' are the same alkyl or phenylalkyl group, a compound of the general formula [ chemical formula 19], and R3 is a compound of the general formula [ chemical formula 20 ].

19. The optical information recording medium according to claim 11, wherein A which is a compound of the general formula [ chemical formula 1] is a compound of the general formula [ chemical formula 2], A 'is a compound of the general formula [ chemical formula 6], m and 1, R, R' are the same alkyl or phenylalkyl group, a compound of the general formula [ chemical formula 19], and R3 is a compound of the general formula [ chemical formula 20 ].

20. The optical information recording medium as claimed in claim 16, wherein A which is a compound of the general formula [ chemical formula 1] is a compound of the general formula [ chemical formula 2], A 'is a compound of the general formula [ chemical formula 6], m and 1, R, R' are the same alkyl or phenylalkyl group, a compound of the general formula [ chemical formula 19], and R3 is a compound of the general formula [ chemical formula 20 ].