CN101171634A

CN101171634A - Optical recording medium, sputtering target and azo-metal chelate dye

Info

Publication number: CN101171634A
Application number: CNA2006800148106A
Authority: CN
Inventors: 内田直幸; 星野博幸; 古村充史; 国府田直树; 今川明彦
Original assignee: KOYA METALS CO Ltd; Mitsubishi Chemical Corp
Current assignee: KOYA METALS CO Ltd; Mitsubishi Chemical Corp; Mitsubishi Chemical Media Co Ltd
Priority date: 2005-04-28
Filing date: 2006-04-28
Publication date: 2008-04-30
Also published as: TW200710170A; WO2006118266A1

Abstract

There is provided an optical recording medium for high-density recording or high-speed recording having a preferable recording characteristic in a wide range of recording linear velocity and an excellent light resistance. The optical recording medium includes at least a recording layer formed by an organic dye and a reflection layer containing metal arranged on a substrate having a coaxial or a spiral groove. Recording is performed with the minimum mark length not greater than 0.4 [mu]m or with a recording linear velocity not smaller than 35.0 m/s. The guide groove on the substrate has a track pitch not greater than 0.8 [mu]m, a groove width not greater than 0.4 [mu]m, and a recording layer film thickness in the groove not greater than 70 nm. The organic dye single layer forming the recording layer has a dye holding ratio not greater than 70% in Wool scale 5th grade (light resistance test) of the light irradiation condition shown in ISO-105-B02. The differentiation value dR/d lambda(%/nm) of the reflection ratio R of the reflection layer for the wavelength in the air is not greater than 3 in the wavelength band from 300 nm to 500 nm.

Description

Optical recording media, sputtering target and azo-metal chelate dye

Technical field

The present invention relates to optical recording media and the sputtering target that can be used for optical recording media and the azo-metal chelate dye that can utilize laser to write down and read, in more detail, the present invention relates in the line speed record scope of broad, have good recording characteristic and the also excellent optical recording media that high-density recording is employed or high-speed record is used of photostability, and the sputtering target and the azo-metal chelate dye that can be used for optical recording media.

Background technology

Therefore now, various optical recording medias such as CD-R, CD-RW, DVD-R, DVD-RW can be stored high capacity information, and random access is easy, as the external memory of signal conditioning packages such as computing machine and by extensive understanding and popularizing.Because the further increase of the quantity of information of handling, people wish to improve recording density.

Especially among various optical recording medias, the optical recording media that CD-R or DVD-R etc. has the recording layer that contains organic dyestuff is more cheap, and has and read the interchangeability of special-purpose optical recording media, has therefore obtained using especially widely.

Generally speaking; present optical recording media is a laminated structure; this laminated structure is; on the transparent optical disc board, has the recording layer that constitutes by alloy firm layer, the thin layer etc. that contains organic dyestuff; have the reflection horizon across this recording layer in a side opposite, and have the protective seam that covers these recording layers or reflection horizon with substrate.Described optical recording media utilizes laser to see through substrate and writes down and read.

The metal or alloy film generally as described reflection horizon (referring to patent documentation 1), especially uses the situation of gold, silver or silver alloy etc. more.Therefore mainly contain silver in these alloys,, and can obtain high reflectance, practicability at present because silver is more cheap.

In addition, about aldary, for example, put down in writing the reflection horizon of containing silver-aldary or silver-palladium-aldary in the patent documentation 2.Record in the patent documentation 3, the alloy firm that will have in copper less than 40% silver is arranged on the reflection horizon.The aldary reflection horizon and the target that contain Ag and Ti have been put down in writing in the patent documentation 4.But these all are the examples less than the optical recording media of the low linear speed writing speed of 2.0m/s.What in addition, these documents related to is the lower optical recording media of recording density.

Patent documentation 1: special fair 7-105065 communique

Patent documentation 2: the spy opens flat 4-49539 communique

Patent documentation 3: the spy opens flat 4-364240 communique

Patent documentation 4: the international WO2002/021524 pamphlet that discloses

Summary of the invention

In recent years, in the densification of recording density, the high-speed recordization of driving is also in development.High-speed record up to 28m/s has been applied to DVD-R, and more high-speed record function development is quickened.The problem that exists in this high-speed record is the nargin that can not obtain writing down (margin).This problem shows as, and for example, when the scope of the recording power that can obtain good record wow and flutter (jitter) value narrows down, or when the recording power increase is write down, has observed the phenomenon that the distortion of waveform takes place in record mark.

Made the present invention in view of the above problems.

That is, purpose of the present invention is, the optical recording media that a kind of high-density recording is employed or high-speed record is used is provided, and described optical recording media has good recording characteristic in the line speed record scope of broad, and " on actual the use " photostability is also excellent.

In addition, other purpose of the present invention is that a kind of optical recording media of suitable high-speed record is provided.

In addition, other purpose of the present invention is, a kind of sputtering target is provided, and this sputtering target is used to make the reflection horizon of the optical recording media of photostability and recording characteristic excellence.

In addition, other purpose of the present invention is, a kind of specific organic dyestuff is provided, and this organic dyestuff can be used for being fit to the recording layer of the optical recording media of high-speed record.

In view of the above problems, the inventor furthers investigate, and found that the following fact, thereby has finished the present invention.Promptly, adjust the composition of dyestuff, make and form in the situation of individual layer at the organic dyestuff that will form recording layer, in the recording layer that low speed uses in recording medium, dyestuff conservation rate before and after the light fastness test is more than 80%, more preferably more than 90%, and in the situation that is used for high density recording or high-speed record, this dyestuff conservation rate is reached be required to be in the actual use enough good below 70%.In addition, use following reflection horizon, the consisting of of described reflection horizon, in the wavelength coverage of 300nm～500nm, the aerial reflectivity R in reflection horizon reaches below 3 the differential value dR/d λ (%/nm) of wavelength X.The inventor finds, by these combinations, has not only realized good recording characteristic in high-speed record but also in the line speed record scope of broad, and has obtained " reality is used " optical recording media that photostability is also excellent.

Promptly, main points of the present invention are a kind of optical recording media, described optical recording media has on the substrate with concentric circles or spiral helicine groove at least by organic dyestuff recording layer that constitutes and the reflection horizon of containing metal, its the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s, it is characterized in that, the track space of the gathering sill on the aforesaid substrate is below the 0.8 μ m, groove width is below the 0.4 μ m, recording layer thickness in the groove is below the 70nm, in the Wool scale of the rayed condition that ISO-105-B02 provides 5 grades (light fastness test), the dyestuff conservation rate of following definitions that forms the organic dyestuff individual layer of above-mentioned recording layer is below 70%, in the wavelength coverage of 300nm～500nm, the aerial reflectivity R in above-mentioned reflection horizon is below 3 to the differential value dR/d λ (%/nm) of wavelength X.

[dyestuff conservation rate]

The dyestuff conservation rate is, in the wavelength coverage of 300nm～800nm, in the maximum absorption wave strong point of the coated film of the organic dyestuff individual layer that forms above-mentioned recording layer, the ratio of the absorbance before and after the above-mentioned light fastness test, that is { (test back absorbance)/(absorbance before the test) } * 100 (%).

In addition, another main points of the present invention are a kind of optical recording media, this optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s, it is characterized in that above-mentioned recording layer contains azo-metal chelate dye that the metallic ion by the azo based compound of following general formula (1) expression and Zn constitutes at least as organic dyestuff.

(1)

(in general formula (1), R ¹Expression hydrogen atom or with CO ₂R ³The ester group of expression (at this, R ³The alkyl or the naphthenic base of expression straight or branched).R ²The alkyl of expression straight or branched.X ¹With any one represents NHSO at least among the X2 ₂Y base (at this, Y represents to have the alkyl of at least 2 substituent straight or brancheds of fluorine atom), X simultaneously ¹And X ²Among another group represent hydrogen atom.R ⁴And R ⁵Represent the alkyl of hydrogen atom, straight or branched or the alkoxy of straight or branched independently of one another.R ⁶, R ⁷, R ⁸And R ⁹Represent that independently of one another hydrogen atom or carbon number are 1 or 2 alkyl.In addition, H ⁺From above-mentioned NHSO ₂The Y base breaks away from, and forms NSO ₂Y ^-(feminine gender) base, thus the azo based compound of above-mentioned general formula (1) expression and metallic ion form coordination bond.)

In addition, another main points more of the present invention are a kind of sputtering target, described sputtering target is used for the manufacturing in the above-mentioned reflection horizon of optical recording media, described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, it is characterized in that described sputtering target is made of the material that the following B of composition represents at least.

[forming (B)]

50 at％≤Cu≤97 at％

3 at％≤Ag≤50 at％

0.05 at％≤X≤10 at％

(at this, X represents to be selected from least a kind of element in the group of being made up of Zn, Al, Pd, In, Sn, Cr, Ni, and wherein, the total amount of Cu, Ag and X is below 100 at% (atom %).)

In addition, another main points of the present invention are a kind of azo-metal chelate dye, described azo-metal chelate dye can be used as the above-mentioned organic dyestuff of optical recording media, described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s, it is characterized in that described azo-metal chelate dye is made of the azo based compound of above-mentioned general formula (1) expression and the metallic ion of Zn.

The invention provides and in the line speed record scope of broad, have good recording characteristic and " reality is used " optical recording media that high-density recording is employed or high-speed record is used that photostability is also excellent.

In addition, the invention provides the optical recording media that is fit to high-speed record.

In addition, the invention provides sputtering target, described sputtering target is used to make the reflection horizon of the optical recording media of photostability and recording characteristic excellence.

In addition, the invention provides azo-metal chelate dye, described azo-metal chelate dye is used for the recording layer of the optical recording media of suitable high-speed record.

Description of drawings

Fig. 1 (a)～(c) is the sectional view of the formation of the optical recording media that schematically shows embodiment of the present invention.

Fig. 2 (a), Fig. 2 (b) are the sectional view of the formation of the optical recording media that schematically shows embodiment of the present invention.

Fig. 3 (a) is the curve map of the Wavelength distribution of the refractive index (n) of expression major metal material, Fig. 3 (b) is the curve map of the Wavelength distribution of the attenuation coefficient (k) of expression major metal material, Fig. 3 (c) is for being illustrated in the curve map of the Wavelength distribution of reflectivity in the air, and described reflectivity calculates the reflection horizon (thickness 120nm) of using the major metal material to form.

Fig. 4 (a)～Fig. 4 (d) is the figure of recording characteristic and " reality is used " sunproof measurement result of the optical recording media of representing embodiment 1, embodiment 2 and comparative example 1, Fig. 4 (a) is the curve map of the measurement result of expression recording power nargin, Fig. 4 (b) is the curve map of the measurement result of expression asymmetry nargin, Fig. 4 (c) is the curve map of the measurement result before and after the light fastness test of expression background wow and flutter (bottom jitter), and Fig. 4 (d) is the curve map of the measurement result before and after the light fastness test of expression PI max.

Fig. 5 (a)～Fig. 5 (d) is the figure of recording characteristic and " reality is used " sunproof measurement result of the optical recording media of representing embodiment 3 and comparative example 2, Fig. 5 (a) is the curve map of the measurement result of expression recording power nargin, Fig. 5 (b) is the curve map of the measurement result of expression asymmetry nargin, Fig. 5 (c) is the curve map of the measurement result before and after the light fastness test of expression background wow and flutter, and Fig. 5 (d) is the curve map of the measurement result before and after the light fastness test of expression PI max.

Fig. 6 (a), Fig. 6 (b) are the figure of measurement result of recording characteristic of the optical recording media of expression embodiment 4 and comparative example 3, Fig. 6 (a) is the curve map of the measurement result of expression recording power nargin, and Fig. 6 (b) is the curve map of the measurement result of expression asymmetry nargin.

Fig. 7 (a)～(d) is the figure of recording characteristic and " reality is used " sunproof measurement result of the optical recording media of representing comparative example 4, Fig. 7 (a) is the curve map of the measurement result of expression recording power nargin, Fig. 7 (b) is the curve map of the measurement result of expression asymmetry nargin, Fig. 7 (c) is the curve map of the measurement result before and after the light fastness test of expression background wow and flutter, and Fig. 7 (d) is the curve map of the measurement result before and after the light fastness test of expression PI max.

Fig. 8 is the curve map of Wavelength distribution that is illustrated in the reflectivity of the metallic reflector individual layer that uses in each embodiment and the comparative example.

Fig. 9 (a)～(d) is the curve map of the value of the dR/d λ that is illustrated in the metallic reflector individual layer that uses in each embodiment and the comparative example.The value of Fig. 9 (a) expression Cu reflection horizon individual layer (embodiment 1), the value of Fig. 9 (b) expression Au reflection horizon individual layer (embodiment 2), the value of Fig. 9 (c) expression Ag reflection horizon individual layer (comparative example 1), the value of Fig. 9 (d) expression Al reflection horizon individual layer (embodiment 5).

Figure 10 is with the CuAg that obtains among the embodiment 6 _12.8And CuAg _12.9Pd _0.7The curve map represented of the measurement result of the Ag, the Au that in embodiment 5, obtain of the measurement result of reflectivity, Cu.

Figure 11 (a), Figure 11 (b) are respectively expression CuAg _12.8And CuAg _12.9Pd _0.7The curve map of result of calculation of dR/d λ.

The curve map of the content of the Ag that Figure 12 obtains among the embodiment 6 for expression and the peaked relation of the dR/d λ in the wavelength coverage of 300nm～500nm.

Figure 13 is the figure that is expressed as follows relation: when supposing that the content substantial linear of photostability and Ag is relevant, and Cu _(100-X)Ag _XIn the value (content of Ag) of X and the relation of background quiver value.

Figure 14 (a), Figure 14 (b) are the result's of the light fastness test among the expression embodiment 6～8 curve map, Figure 14 (a) is the curve map of the relation of expression xenon lamp irradiation time and quiver value, and Figure 14 (b) is the curve map of the relation of expression xenon lamp irradiation time and PI mistake.

Figure 15 (a), Figure 15 (b) are the result's that hot and humid down the storage stability of expression among the embodiment 6～8 test curve map, Figure 15 (a) is the curve map of the time variation of expression quiver value, the curve map that Figure 15 (b) changed for the time of representing the PI mistake.

Symbol description

11,12,22 fit with dish

21 virtual disks

100,200,300,400,500 optical recording medias

101,201,401,501 substrates (1)

102,402,502 recording layers (1)

103,202,403,503 reflection horizon (1)

104,203 protective finish (1)

105,204,407,504 tack coats

106,205 protective finish (2)

107,206,406,506 reflection horizon (2)

108,405,505 recording layers (2)

109,208,408,507 substrates (2)

110,111,210,310,410,510 laser

207,303 recording layers

301 substrates

302 reflection horizon

304,508 barrier layers

305,404,504 transparent resin layers (middle layer), tack coat (middle layer)

Embodiment

Below, the specific embodiment of the present invention (hereinafter referred to as the working of an invention mode) is elaborated.Certainly, the present invention is not limited to following embodiment, can carry out various distortion in the scope of its main points and implement.

[I. key concept 1 of the present invention]

In the present invention, a kind of optical recording media at first is provided, this optical recording media has on the substrate with concentric circles or spiral helicine groove at least by organic dyestuff recording layer that constitutes and the reflection horizon of containing metal, the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s, it is characterized in that, the track space of the gathering sill on the aforesaid substrate is below the 0.8 μ m, groove width is below the 0.4 μ m, recording layer thickness in the groove is below the 70nm, in the Wool scale of the rayed condition that ISO-105-B02 provides 5 grades (light fastness test), the dyestuff conservation rate of following definitions that forms the organic dyestuff individual layer of above-mentioned recording layer is below 70%, in the wavelength coverage of 300nm～500nm, the airborne reflectivity R in above-mentioned reflection horizon is (below, be referred to as " the 1st optical recording media of the present invention " sometimes) below 3 to the differential value dR/d λ (%/nm) of wavelength X.

In order to have the optical recording media that high-density recording is employed or high-speed record is used of good recording characteristic in the line speed record scope that is provided at broad, the inventor furthers investigate.

In addition, " high density recording " among the present invention is with the be recorded as prerequisite of the shortest mark length less than the density of 0.4 μ m.This is because by shortening record mark, reduce track space and in by the optical recording media of densification, it is remarkable especially that the problem of Xie Decision is Yaoed in this invention.In " high density recording ", it is important reducing excessive recording portion formation.

In addition, " high-speed record " among the present invention is meant with the record more than the line speed record 35.0m/s (with DVD is example, the record under the rotating speed more than 10 times of 1 times of speed (being linear speed 3.5m/s) of DVD).

In addition, the record of the 1st optical recording media of the present invention is equivalent in the situation of " high-speed record ", " high density recording " that can be not necessarily above-mentioned, that is and, not necessarily the shortest mark length is less than the record of the density of 0.4 μ m.But even in this case, also preferably carry out record with the shortest mark length for the density of following scope: the shortest mark is long usually less than 0.5 μ m, is preferably below the 0.44 μ m, more preferably below the 0.4 μ m.

The inventor discovers, as the dyestuff that is used for recording layer (dye coating), has suitable dyestuff or dye combinations.Promptly, dyestuff conservation rate behind the light fastness test of service recorder layer individual layer is the dyestuff below 70%, perhaps mixing " dyestuff of photostability difference " and " dyestuff that photostability is good ", is below 70% thereby make the dyestuff conservation rate of the light fastness test front and back of recording layer individual layer.

But known being suitable for, carried out the dyestuff of high-speed record or dye combinations produces new problem with described high density, promptly causes the photostability deterioration of CD.

The inventor further studies this new problem.It found that, below 3, can solve above-mentioned new problem to the differential value dR/d λ (%/nm) of wavelength X by making the aerial reflectivity R in reflection horizon.Promptly, can make " on actual the use " the photostability raising.In addition, " reality is used " photostability among the present invention is meant following index: although good inadequately in the photostability of recording layer individual layer, but when constituting CD, the light time that irradiation Wool scale is 5 grades, whether the wow and flutter of the recording section of CD or mistake be in preferred range.Thereby its index with the dyestuff conservation rate of recording layer itself is distinguished mutually.

Promptly, in key concept 1 of the present invention, optical recording media has on the substrate with concentric circles or spiral helicine groove at least by organic dyestuff recording layer that constitutes and the reflection horizon of containing metal, the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s, it is characterized in that, groove width on the aforesaid substrate is below the 0.4 μ m, recording layer thickness in the groove is below the 70nm, in the Wool scale of the rayed condition that ISO-105-B02 provides 5 grades (light fastness test), the dyestuff conservation rate that forms the organic dyestuff individual layer of recording layer is below 70%, in the wavelength coverage of 300 nm～500 nm, the airborne reflectivity R in above-mentioned reflection horizon is below 3 to the differential value dR/d λ (%/nm) of wavelength X.

Be meant following ratio at this " dyestuff conservation rate ": in the wavelength coverage at 300nm～800nm, the ratio of the absorbance before and after the above-mentioned light fastness test of the maximum absorption wave strong point of the coated film of the organic dyestuff individual layer of formation recording layer, i.e. { (test back absorbance)/(the preceding absorbance of test) } * 100 (%).

In addition, be below the 0.4 μ m by the groove width that makes substrate, can reach track space is the following densification of 0.8 μ m, guaranteed enough push-pull signal amplitudes simultaneously, therefore, as mentioned above, in the situation about writing down with the high speed rotating CD, can stably on groove, follow rail.In addition, on the basis of guaranteeing enough push-pull signal amplitudes, groove width is generally more than the 0.1 μ m, more preferably more than the 0.2 μ m.In addition, track space is made as more than the 0.2 μ m usually, preferably is made as more than the 0.4 μ m.

In addition, be below the 70nm by making the recording layer thickness in the groove, can suppress to form excessive recording portion, minimizing is crosstalked, and realizes good " high density recording " and " high-speed record ".In addition, the thickness of the recording layer in the groove is generally more than the 5nm, more preferably more than the 10nm, more preferably more than the 20nm.

In above-mentioned high-speed record, usually, must be with the extremely short the shortest mark of pulse shaping of the irradiation time of laser.That is, in described high-speed record, the record that is used for the shortest mark of record long (example for present embodiment is the 3T mark) uses laser irradiation time less than 8ns (nanosecond).Therefore, in described high-speed record, can write down and be meant, under the record condition of laser irradiation time when the long record of the shortest mark less than 8ns, can under background wow and flutter (minimum value of quiver value) is no more than 9% situation, carry out record, perhaps have good error rate (good degree is the problem that reads that does not have in the commercially available reading device).Consider that for example be about 4ns the start-up time of the semiconductor laser of the wavelength coverage of DVD, should " carry out the long record of the shortest mark less than the such short pulse of 8ns " as can be known and be how harsh record condition with irradiation time.

In addition, under 10 times of speed recordings (35m/s) and 16 times of speed recordings (56.0m/s), the wide 7.9ns of being respectively of radiation pulses and the 6.5ns of the long recording laser of the 3T mark that in each embodiment described later and comparative example, uses.

In addition, in the present invention, " can in the line speed record scope of broad, write down well " and be meant, (with DVD is example at 3.5m/s～about 70m/s, 1 times of speed recording (3.5m/s) of DVD～about 20 times of speed recordings (70m/s)) in, can under the background wow and flutter is no more than 9% situation, carry out record, perhaps have good error rate (good degree is the problem that reads that does not have in the commercially available reading device).For example, on DVD-R, for the evaluation of record quality, quiver value is good index.For example, according to the scope known at present, generally speaking, following situation is judged as good especially: at 3.5m/s～28m/s (for example, for DVD is 1 times of speed recording～8 times speed recording) in, the background wow and flutter of available record is generally below 8.0%, more preferably below 7%, more preferably below 6%.

The inventor furthers investigate, and the result thinks that the problem of the record nargin in the above-mentioned problem can solve by following means: reduce the writing speed interdependence of organic dyestuff medium, and increase the response to short pulse.

More particularly, according to the inventor's research as can be known, by in recording layer, comprising " dyestuff of photostability difference ", can in the writing speed scope of broad, guarantee good recording characteristic, that is, sunproof deterioration degree and high-speed record characteristic, the recording characteristic in the writing speed scope of broad are relevant.Can think that the reason of this effect is that " dyestuff of photostability difference " can more effectively utilize the luminous energy (optical mode) as recording smooth incident by the decomposition of dyestuff.That is, can think that in described dyestuff, optical mode participates in the cleavage reaction of key of dyestuff, and uses luminous energy expeditiously, form the precipitous record mark in edge, thereby recording characteristic can improve.Perhaps, the reaction velocity of general optical mode record is well-known soon, can (order of magnitude of fsec～psec) makes reaction terminating with femtosecond～psec on the principle.As long as reaction stops with this order of magnitude time, then consider from the rotational speed of CD, do not take place and adjacent marker between possibility of interference high.

On the other hand, will be commonly referred to as the heat pattern record by the light of incident as the situation that thermal energy is used for the reaction (comprising decomposition, fusion) of dyestuff as recording light.

Can think, in this heat pattern record, have the limit by the reaction velocity of heat conduction velocity decision, in DVD-R for example, reaction stops with the ns order of magnitude usually.If reaction stops with this order of magnitude, then the order of magnitude of disk rotation speed and reaction velocity is a same levels, and therefore the influence of heat can reach adjacent marker.If the influence of heat reaches adjacent marker, so-called heat then takes place between mark interfere, and the possibility that wow and flutter is worsened raises.But, it is believed that it doesn't matter for this heat pattern and photostability, therefore " dyestuff that photostability is good " mainly decomposes with this pattern, and is recorded.

In addition, can think, by in described " dyestuff of photostability difference ", mixing " dyestuff that photostability is good ", the physical change of balance recording section and optical change dexterously, and can further improve the high-speed record characteristic.Can think, this be because, " dyestuff of photostability difference " has the tendency that above-mentioned heat pattern record does not take place substantially, can not be write down degree of modulation fully with " dyestuff of photostability difference ", for example, can utilize big " dyestuff that photostability is good " of tendency that the heat pattern record takes place that it is remedied.

Can think that above-mentioned " dyestuff of photostability difference " is from the little dye composition of probability of happening with the what is called " radiationless transition " of light activated state.Can enumerate, for example, (1) not only have be considered to the record and read wavelength near participate in π-π ^*The strong absorption band of transition or charge transfer transition etc., and the dyestuff of the good structure of planarity (not having a large amount of steric configuration (configuration)).As suitable therewith dyestuff, can enumerate easy generation π-π ^*Transition and send numerous organic dyestuff of fluorescence mostly, but as the dyestuff that is fit to CD, can enumerate, for example, the specific cyanine based dye of below enumerating.In addition, it is good that metal chelate dye is considered to photostability always, even but among this metal chelate dye, can think also that (2) have that central metal is subjected to the effect of light and the metal chelate dye of the tendency that is easy to break away from from coordination bond is equivalent to " dyestuff of photostability difference ".About (2), as zinc, in the situation that central metallic ions does not have in the situation of empty d track in should participating in the outermost d track of coordination bond or empty d track is less (in the present invention, for example, Zn ²⁺Because electron configuration 3d from Zn ¹⁰4s ²(by ionization) removed 2 electronics and got 3d ¹⁰Electron configuration), the covalent bond of metal-ligand diminishes.In addition, make electronics be excited to ligand by optical excitation, central metal has the tendency of easy disengaging.Its result, absorption band blue shift, and optical constant sometimes changes.In addition, the ligand that breaks away from from coordination bond is the situation of ligand of photostability difference, its ligand increases with the tendency that optical mode reacts, therefore, can think, identical with " dyestuff of photostability difference " of the type of (1), the decomposition reaction of described dyestuff has the tendency of optical mode record.Thereby, as the central metal of such " the photostability difference " metal chelate dye, belong to owing to ionization makes empty d track less or be not the free such metal of d track.In addition, also preferred ligand has the molecular orbit (for example, ligand has the π track (anti-bonding orbital) of the antibonding of sky) that easy generation MLCT (the metal-ligand lotus moves transition) waits.In addition, for the size of the contribution of optical mode in the decomposition of these dyestuffs, also can infer according to whether sending fluorescence.That is, can think that the dyestuff that sends fluorescence has the bigger tendency of the contribution of optical mode in the decomposition.In addition, also can think, although central metallic ions is got d ⁹Or d ¹⁰Electron configuration, but ligand and the less such character of central metal ion covalent bond (coordination bond is strong) also can be associated near 0 with structure choice.In addition, for above-mentioned " structure choice energy ", with reference to K.F.Puncell et al., Inorganic Chemistry, 1977, p.550.

On the other hand, in " dyestuff that photostability is good ", can enumerate, for example, the big dye composition of probability that radiationless transition takes place.In described dye composition, absorbed light mainly is converted to thermal energy.About described metal chelate dye, can enumerate d track free in its central metal ion d track for example or can obtain the azo-metal chelate dye of first transitional element (3d transitional element) of empty d track.The overlapping hybrid orbital that forms of the d track of the sky by metallic ion and the track of ligand, the covalent bond of metal-ligand is big, even thereby in excited state, the possibility that forms the stable chelate structure is also very big.That is, can think,, also can not cause ligand to break away from from coordination bond even be subjected to optical excitation.

As the example of above-mentioned " dyestuff of photostability difference ", can enumerate, with Zn the azo complex compound of central metal or the cyanine based dye that does not contain quencher etc.In addition,, also can use the azo complex compound as central metal with Cu or Ni etc. according to the difference of the kind of ligand, but preferred especially is the azo complex compound of central metal with Zn.As the example of described dyestuff, can enumerate, the metal chelate dye of 2 following azo based compounds of 1 Zn element coordination.

In addition, " dyestuff of photostability difference " among the present invention is meant, in the independent composition of this dyestuff, the dyestuff conservation rate of the present invention's regulation is preferably the dyestuff below 70%.Because the dyestuff conservation rate of " dyestuff of photostability difference " is little of falling in this scope, thereby for the foregoing reasons, it can have the characteristic of excellence under high-speed record or high density recording, so it is preferred.

In addition, " dyestuff that photostability is good " among the present invention is meant, in the independent composition of its dyestuff, the dyestuff conservation rate of the present invention's regulation is preferably greater than 70% dyestuff.More preferably more than 80%, more preferably more than 85%.

For as above-mentioned " dyestuff of photostability difference " and the example of preferred azo complex compound, can enumerate, the azo-metal chelate dye that constitutes by the metallic ion of the azo based compound of following general formula (1) expression and Zn (below, be called " dyestuff (1) " in the time of suitably).

(1)

In general formula (1), R ¹Expression hydrogen atom or with CO ₂R ³The ester group of expression (at this, R ³The alkyl or the naphthenic base of expression straight or branched).

R ²The alkyl of expression straight or branched.

X ¹And X ²Among at least any one the expression NHSO ₂Y base (at this, Y represents to have the alkyl of at least 2 substituent straight or brancheds of fluorine atom), X simultaneously ¹And X ²Among another group represent hydrogen atom.

R ⁴And R ⁵Represent the alkyl of hydrogen atom, straight or branched or the alkoxy of straight or branched independently of one another.

R ⁶, R ⁷, R ⁸And R ⁹Represent that independently of one another hydrogen atom or carbon number are 1 or 2 alkyl.

In addition, H ⁺From above-mentioned NHSO ₂The Y base breaks away from, and forms NSO ₂Y ^-(feminine gender) base, thus the azo based compound of above-mentioned general formula (1) expression and metallic ion form coordination bond.

As R ³Preferably, carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, sec-butyl are 1～8 the straight chain or the alkyl of side chain; Carbon numbers such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl are 3～8 naphthenic base.From sterically hindered little such reason, particularly preferably be carbon numbers such as methyl,

ethyl

1 or 2 straight chained alkyl; Carbon number such as cyclopentyl, cyclohexyl is 3～6 naphthenic base.

As R ²Can preferably enumerate carbon numbers such as methyl, ethyl, propyl group, butyl, amyl group, hexyl and be 1～8 straight chained alkyl; Carbon numbers such as isopropyl, sec-butyl, isobutyl, the tert-butyl group, 2-ethylhexyl, cyclopropyl, cyclohexyl methyl are 3～8 branched alkyl etc.

Y represents to have the alkyl of at least 2 substituent straight or brancheds of fluorine atom.As the alkyl of straight or branched preferably carbon number be the alkyl of 1～6 straight or branched, more preferably carbon number is 1～3 straight chained alkyl.

As R ⁴, R ⁵, preferably hydrogen atom, carbon number are that 1～6 straight chained alkyl, carbon number are 1～8 alkoxy.As R ⁴, R ⁵, more preferably hydrogen atom, carbon number are that 1 or 2 alkyl or carbon number are 1 or 2 alkoxy.Abovementioned alkyl, the preferred unsubstituted of alkoxy.As R ⁴, R ⁵, particularly preferably be hydrogen atom, methyl, ethyl or methoxyl.

R ⁶, R ⁷, R ⁸And R ⁹Represent that independently of one another hydrogen atom or carbon number are 1 or 2 alkyl.By using hydrogen atom or carbon number is 1 or 2 alkyl, be easy to absorbance or refractive index are adjusted to predetermined value, and be preferred therefore.About carbon number is 1 or 2 alkyl, can replace with other substituting group (for example halogen atom) with the hydrogen atom of carbon atom bonding, but the alkyl of preferred unsubstituted.As carbon number is 1 or 2 alkyl, can enumerate methyl, ethyl.Consider from synthetic easiness or spatial structure aspect, as R ⁶, R ⁷, R ⁸And R ⁹Hydrogen atom most preferably.

As the concrete example of the azo based compound (ligand) of the general formula (1) that constitutes described dyestuff (1), can enumerate the azo based compound of structure shown below.

On the other hand, as the example of above-mentioned " dyestuff of photostability difference " preferred cyanine based dye, can enumerate the cyanine based dye (below, be called " dyestuff (2) " in the time of suitably) of following general formula (2) expression.

(2)

In the general formula (2), ring A and ring B represent to have substituent phenyl ring or naphthalene nucleus independently of one another.

R ¹⁰And R ¹¹It is 1～5 alkyl that expression independently of one another can have substituent carbon number.

R ¹², R ¹³, R ¹⁴And R ¹⁵It is 1～5 alkyl that expression independently of one another can have substituent carbon number.

R ¹⁶Expression hydrogen atom, halogen atom, cyano group or can to have substituent carbon number be 1～5 alkyl.

Q ^-The expression counter anion.As counter anion, can enumerate BF ₄ ^-, PF ₆ ^-, various negative ion such as metal complex.

As R ¹⁰And R ¹¹, preferably carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, sec-butyl are 1～5 the straight chain or the alkyl of side chain.From sterically hindered little such reason, particularly preferably be carbon numbers such as methyl, ethyl and be 1 or 2 straight chained alkyl.In addition, the hydrogen atom of alkyl chain can be replaced by fluorine or substituting group described later.

As R ¹², R ¹³, R ¹⁴And R ¹⁵, preferably can enumerate carbon numbers such as methyl, ethyl, propyl group, butyl, amyl group and be 1～5 straight chained alkyl; Carbon numbers such as isopropyl, sec-butyl, isobutyl, the tert-butyl group are 3～5 branched alkyl etc.In addition, the hydrogen atom of alkyl chain can be replaced by fluorine or substituting group described later.

As R ¹⁶, hydrogen atom preferably; Halogen atom such as Cl, Br; Cyano group; Carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, sec-butyl are 1～5 the straight chain or the alkyl of side chain.In addition, use in the situation of alkyl, the hydrogen atom of alkyl chain can be replaced by substituting group described later.

In addition, as ring A and the ring phenyl ring of B or the preferred substituents of naphthalene nucleus, can enumerate: carbon number be 1～6 straight chain or side chain alkyl,

Carbon number be 1～12 aryl or heteroaryl (carbon number is 1～12 carbon-ring type or hetero ring type aryl),

Carbon number be 1～6 alkoxy,

Carbon number be 1～6 ester group,

Carbon number be 1～6 dialkyl amido,

Nitro,

Carbon number be 1～6 alkylthio,

Carbon number be 1～6 alkyl sulphonyl,

Carbon number be 1～6 trialkylsilkl,

Sulfonic group,

Phosphate,

The carboxylic acid group,

Cyano group,

Halogen atom etc.

In addition, as R ¹⁰To R ¹⁶Alkyl on preferred substituents, can enumerate: carbon number be 1～12 aryl or heteroaryl (carbon number is 1～12 carbon-ring type or hetero ring type aryl),

Carbon number be 1～6 alkoxy,

Carbon number be 1～6 ester group,

Carbon number be 1～6 dialkyl amido,

Nitro,

Carbon number be 1～6 alkylthio,

Carbon number be 1～6 alkyl sulphonyl,

Carbon number be 1～6 trialkylsilkl,

Sulfonic group,

Phosphate,

The carboxylic acid group,

Cyano group,

Halogen atom etc.

As above-mentioned substituting group preferably carbon number be 1～12 carbon-ring type or hetero ring type aryl.More preferably carbon number is 6～12 carbon-ring type aryl.Consider from the recording characteristic aspect, further preferably phenyl ring.

Consider from the recording characteristic aspect, most preferably, be used for R ¹²～R ¹⁶The part of alkyl in, preferably use the hydrogen of phenyl ring substituted alkyl chain.Specifically, as phenyl ring is used as substituent method, the combination that can enumerate following (α)～(γ).If consider sterically hindered etc., preferably with (α) and being used in combination (β).(α) with R ¹², R ¹³In the situation for alkyl, utilize phenyl ring to replace R ¹², R ¹³One of or both hydrogen of alkyl chain.

(β) with R ¹⁴, R ¹⁵In the situation for alkyl, utilize phenyl ring to replace R ¹⁴, R ¹⁵One of or both hydrogen of alkyl chain.

(γ) with R ¹⁶In the situation for alkyl, utilize phenyl ring to replace R ¹⁶The hydrogen of alkyl chain.

As the concrete example of described dyestuff (2), can enumerate the compound of structure shown below.

In addition, above-mentioned " dyestuff of photostability difference " in the recording layer can use any one separately, also can use two or more with combination in any.Wherein, preferably use a kind of above-mentioned dyestuff (1) and/or dyestuff (2) at least.In this case, can only use any one or two or more above-mentioned dyestuffs (1), also can only use any one or two or more above-mentioned dyestuffs (2), further can also be aptly any one or two or more above-mentioned dyestuff (1) and any one or two or more above-mentioned dyestuffs (2) be used in combination.Certainly, except that above-mentioned dyestuff (1) and/or dyestuff (2), further can also be used in combination other " dyestuff of photostability difference ".

On the other hand, as with preferred " dyestuff that photostability is good " of above-mentioned dyestuff (1) or dyestuff (2) combination, specifically, can enumerate, the coordination of 2 various azo based compounds, be the metal azo complex compound of central metal with the transition metal except that Zn (for example V, Cr, Mn, Fe, Co, Ni, Cu).The central metallic ions that is preferably formed coordination bond is the divalent ion.

Preferably can enumerate by the azo-metal chelate dye of the metallic ion formation that is selected from least a azo based compound in the group of forming by the compound of following general formula (3), (4), (5), (6) expression and the 3d transitional element except that Zn (below, the azo-metal chelate dye that will have sometimes corresponding to the azo based compound of each general formula is called " dyestuff (3) ", " dyestuff (4) ", " dyestuff (5) ", " dyestuff (6) ").

(3)

In general formula (3) and (5), R ²⁰The expression hydrogen atom, can have the alkyl that substituent carbon number is 1～6 straight chain, side chain or ring-type, perhaps expression can have the ester group that substituent carbon number is 1～6 the alkyl with straight chain, side chain or ring-type.

In general formula (4) and (6), R ¹⁷It is 1～6 alkyl that expression can have substituent carbon number.

R in general formula (3) and (4) ²¹To R ²⁷And the R in general formula (5) and (6) ¹⁸And R ¹⁹Represent hydrogen atom independently of one another, can have the alkyl that substituent carbon number is 1～6 straight chain, side chain or ring-type.R ¹⁸And R ¹⁹Also bonding and form ring mutually.

In general formula (3), (4), (5), (6), X ¹And X ²Among at least any one the expression NHSO ₂Y base (at this, Y represents to have the alkyl of at least 2 substituent straight or brancheds of fluorine atom), X simultaneously ¹And X ²Among another group represent hydrogen atom.

In addition, H ⁺From above-mentioned NHSO ₂The Y base breaks away from, and forms NSO ₂Y ^-(feminine gender) base, thus the azo based compound and the metallic ion of above-mentioned general formula (3), (4), (5), (6) expression form coordination bond.

As R ¹⁷, preferably carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, sec-butyl are 1～6 the straight chain or the alkyl of side chain.

As R ¹⁸, R ¹⁹, preferably can enumerate carbon numbers such as methyl, ethyl, isopropyl, propyl group, isopropyl, butyl, isobutyl, amyl group, hexyl and be 1～6 the straight chain or the alkyl of side chain.In addition, R ¹⁸, R ¹⁹Also bonding and form the cyclic alkyls such as cyclohexyl of ring-type mutually.

As R ²⁰, preferably: hydrogen atom; Carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, amyl group, hexyl are 1～6 the straight chain or the alkyl of side chain; It is 1～6 the straight chain or the ester group of cyclic alkyl that carbomethoxy, ethoxycarbonyl, propyl ester base, isopropyl ester base, butyl ester base, isobutyl ester group, pentyl ester base, hexamethylene ester group etc. have carbon number.Be easy to carry out the synthetic and recording characteristic of industry etc. if take all factors into consideration, as R ²⁰Particularly preferably be hydrogen atom.

As R ²¹To R ²⁷, preferably can enumerate: hydrogen atom; Carbon numbers such as methyl, ethyl, isopropyl, propyl group, isopropyl, butyl, isobutyl, amyl group, hexyl are 1～6 the straight chain or the alkyl of side chain.

As X ¹, X ²And it is Y, as long as identical with the azo based compound of general formula (1) expression.

In addition, as the R that can substitute onto above-mentioned general formula (3), (4), (5), (6) ¹⁷～R ²⁷Alkyl on substituting group, can enumerate:

Carbon number be 1～6 alkoxy,

Carbon number be 1～6 ester group,

Carbon number be 1～6 dialkyl amido,

Nitro,

Carbon number be 1～6 alkylthio,

Carbon number be 1～6 alkyl sulphonyl,

Carbon number be 1～6 trialkylsilkl,

Cyano group,

Halogen atom etc.

As the concrete example of the azo based compound (ligand) of the general formula (3) that constitutes described azo-metal chelate dye, (4), (5), (6), can enumerate the compound of structure shown below.

In addition, above-mentioned " dyestuff that photostability is good " can use any one separately, also can use two or more with combination in any.Especially preferably use a kind of above-mentioned dyestuff (3), dyestuff (4), dyestuff (5) and/or dyestuff (6) at least.In this case, can use one or more only corresponding to dyestuff one of any among above-mentioned dyestuff (3), (4), (5) and (6), select one or more dyestuff to be used in combination respectively above-mentioned dyestuff (3) that also can be more than two classes, (4), (5) and (6).Certainly, except that above-mentioned dyestuff (3), dyestuff (4), dyestuff (5) and/or dyestuff (6), can also further make up other " dyestuff that photostability is good ".

The above-mentioned photostability index to the clear and definite dyestuff of recording characteristic effect will be described below.That is, in the situation of " dyestuff of photostability difference " that will constitute recording layer and " dyestuff that photostability is good " and usefulness, the blending ratio of these dyestuffs is carried out following control.That is, mix with following ratio: the rayed condition (that is, Wool scale is 5 grades) that the dyestuff conservation rate of the described recording layer individual layer organic dyestuff individual layer of recording layer (form) is provided at ISO-105-B02 is issued to the ratio below 70%.

Photostability is better than can not having given play to sufficient optical mode in the situation of this value in decomposition, and therefore, the contribution of the heat pattern in the decomposition of dyestuff (pyrolysis) is big, so that possibly can't expect fully to improve recording characteristic.

In addition, about the dyestuff conservation rate of above-mentioned recording layer individual layer,, in CD section, also can estimate with the method for following embodiment record with the substrate that is exposed and dyestuff even the CD that applying is obtained is peeled off in the fitting part.

As with above-mentioned, on the other hand, the dye combinations as described above that is suitable for high-speed record may make the photostability deterioration of CD.

As the sunproof solution that improves described " dyestuff of photostability difference ", generally speaking, can contain recording sensitivity improving agents such as transition metal chelate compound (for example, acetylacetone chelate, diphenyl two mercaptan, salicylaldoxime, two two sulphur-α-diketone etc.) as singlet oxygen quencher etc. or metal based compound.Be meant at this metal based compound, in compound with atom, ion, bunch etc. form comprise the compound of metals such as transition metal, and can enumerate, for example ethylenediamine is that complex compound, azomethine are that complex compound, phenyl hydramine are that complex compound, phenanthroline are that complex compound, dihydroxy azo benzene series complex compound, dioxime are that complex compound, nitroso-amino-phenol are that complex compound, pyridine radicals triazine are that complex compound, diacetone are that complex compound, metallocene are that complex compound, porphyrin are the such organometallics of complex compound.As metallic atom, have no particular limits, however preferred transition metal.

But by adding described quencher, the abruptness at the edge of record mark may be lost, and perhaps manufacturing process may become complicated.

The inventor does not actively use described adjuvant, has carried out the research that " reality is used " photostability is improved.Its result recognizes, by using following reflection horizon, the photostability of recording layer improved: described reflection horizon in wavelength 300nm≤λ≤500nm scope in air reflectivity R to the differential value (dR/d λ)≤3 of wavelength.

As its reason, can consider as follows.That is based on the free-electron model of metal, for metal, when shining certain specific light frequency, the phenomenon of all resonance of electronics in the metal takes place.If this resonance takes place, then not only refractive index (n) but also reflectivity sharply change with specific frequency.If this electronics all resonates, then with the interface of dyestuff on, the chemical reaction that optical excitation causes (also comprising catalyst reaction) becomes and carries out easily, the possibility of dyestuff deterioration is higher.Therefore, consider that change is unfavorable because of certain specific light frequency makes reflectivity take place sharp from sunproof aspect.According to this result, the condition that not only needs to select the absolute value of reflectivity not change sharp, and the condition that needs to select the relative value of reflectivity not change sharp promptly, need be chosen in the reflection horizon of (dR/d λ)≤3 in the above-mentioned wavelength coverage.As the material that satisfies described condition, can enumerate, for example, can interband transition the material in the scope of 300nm～500nm etc. not.More preferably, (dR/d λ)≤2, further preferred (dR/d λ)≤1.In addition, the reason that the wavelength coverage with the regulation of dR/d λ is made as 300nm～500nm is described below.

Example as the reflection horizon of satisfying described condition, can enumerate following reflection horizon: described reflection horizon contain at least a element that is selected among Cu, Au and the Al (below, sometimes be referred to as " element-specific "), and the total ratio of these element-specific in the reflection horizon is more than 50 at%.Be lower than in the situation of 50 at% in this ratio, might do not satisfy (dR/d λ)≤3 in the above-mentioned wavelength coverage, thereby, sufficient photostability may not be obtained.In addition, as the element except that above-mentioned element-specific in the described reflection horizon, preferably, can enumerate at least a element that is selected from the group of forming by Ag, Cr, Ni, Pt, Ta, Pd, Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, Ti, Zn, Zr and rare earth metal.The ratio of these elements in the preferred especially reflection horizon and the ratio of above-mentioned element-specific amount to 100 at%.The kind of preferably adjusting the element except that element-specific with and combined amount, to satisfy above-mentioned (dR/d λ)≤3.

In addition, also preferred airborne reflectivity in 300nm～500nm scope is 20%～70% reflection horizon.This necessary condition and not only mean use as the prior art only in the record and the high reflection horizon of reflectivity of reading the light wave strong point.Promptly, by using following reflection horizon, " actual use on " photostability of recording layer further improves: described reflection horizon is for record and read optical wavelength high reflectance 80% or more is arranged, and the airborne reflection horizon of while in the wavelength coverage of 300nm～500nm is 20%～70%.

As the reason that the reflection horizon of satisfying described necessary condition is improved the photostability of recording layer, can consider as follows.Originally, the light fastness test (ISO-105-B02) of the CD of implementing usually was the test method that supposition is exposed to sunshine.As everyone knows, sunshine is at 300nm～500nm, particularly intensity reaches capacity in 400nm～500nm scope, and in addition, the energy and the light frequency of light particle are proportional, so the energy of light particle also is higher than the energy of long wavelength's light particle.Have high-octane smooth particle and surpass the probability height of the threshold value of the key that destroys dyestuff, so, it is desirable to, do not make the light of this wavelength of dyestuff taken in excess for the photostability that makes CD improves.That is, preferably use the little reflection horizon of reflectivity in this wavelength coverage.So, can think that as long as use in the little reflection horizon of above-mentioned wavelength coverage internal reflection rate, the light quantity of the multipath reflection between dye recording layer-reflection horizon just obtains reducing, the deterioration of recording layer that therefore has the dyestuff of photostability difference is inhibited.Can further make like this, " on actual the use " the photostability raising.

Fig. 3 (a) is the curve map of the Wavelength distribution of the refractive index (n) of expression major metal material, Fig. 3 (b) calculates the curve map of the Wavelength distribution of aerial reflectivity for the curve map of the Wavelength distribution of the attenuation coefficient (k) of expression major metal material, Fig. 3 (c) to the reflection horizon (thickness 120nm) of using the major metal material to form for expression.In addition, the thickness 120nm in reflection horizon is a fully saturated thickness of reflectivity.In addition, " airborne " reflectivity is meant in this manual, and when by air incident light being shone directly into the face in reflection horizon, the light intensity of reflection is with respect to the ratio of incident intensity.

By Fig. 3 (a) as can be known, with respect to the Ag that is commonly used for the reflection horizon, in the zone of 350nm～500nm, (n) is bigger for the refractive index of Au, Cu and Al.Particularly, the refractive index of Au and Cu (n) is stable in this wavelength coverage, is about 1.In addition, by Fig. 3 (c) as can be known, the reflectivity of Au and Cu is 30%～70%, compare with Ag, and be very little.

In addition, as the refractive index (n) of the metal material in Fig. 3 (a) and (b) and the value of attenuation coefficient (k), the value of using following document to put down in writing.

Springer-Verlag Heidelberg，Landolt Bornstein-Group III Condensed matter，Volume 15，subvolume B，1985，p.222-236(Ag-Ca)，p.237-248(Cd-Eu)，p.280-291(Ni-Pb)(ISSN：1616-9549)

Example as the reflection horizon of satisfying described condition, can enumerate following reflection horizon: at least a element that is selected among Cu, Au and the Al is contained (sometimes in described reflection horizon, be referred to as " element-specific "), the total ratio of these element-specific in the reflection horizon is more than 50 at% simultaneously.Be lower than in the situation of 50 at% in this ratio, might do not satisfy the scope of above-mentioned preferred reflectance.In addition, as the element except that above-mentioned element-specific in the described reflection horizon, preferably can enumerate at least a element that is selected from the group of forming by Ag, Cr, Ni, Pt, Ta, Pd, Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, Ti, Zn, Zr and rare earth metal.The ratio of these elements in the preferred especially reflection horizon and the ratio of above-mentioned element-specific amount to 100 at%.

In addition, by the inventor's result of study as can be known, for example, for the silver or the silver alloy of present practicability, the variation before and after the record in recording layer and reflection horizon is different during with low-speed record, so the above high-speed record of 35.0m/s may become difficult.This be because, can think, particularly surpass in the record of 35.0m/s, owing to the pulse width of the laser that will shine for record shortens, thereby the plastic yield in reflection horizon, thermal conductivity, absorption or the difference that reflects such optical constant are tended to be reflected on the recording characteristic more significantly.Therefore, compare, more will note selection the reflection horizon of described high-speed record purposes with the situation of present low-speed record.But because the actual effect of recording characteristic under low-speed record, or because relatively more cheap, present situation is to be that the optical recording media in reflection horizon drops into practical application widely with silver or silver alloy.

The inventor is through further investigation, found that, the line speed record of (particularly more than the 35.0m/s) at a high speed not only, and the recording characteristic in the line speed record scope of broad from low speed to high speed is according to the reflection horizon and difference, for example, make recording characteristic become good by using as the reflection horizon of major component with copper, gold or aluminium.

Also bring recording characteristic multiple influence to write down at a high speed.Particularly, in the situation that recording layer is made of organic dyestuff, compare the writing speed interdependence highly significant of recording sensitivity, wow and flutter etc. with recording film medium that constitutes by metal or semiconductor etc.Therefore, as the desired condition in reflection horizon that with the organic dyestuff is the medium of recording layer, preferably have the above high reflectance of particular value and have higher heat conducting reflection horizon.The metallic reflective coating that reflectivity is high is meant that promptly, the real part n of the refractive index of marking wave strong point is the following and bigger reflection horizon of imaginary part k of certain value.Specifically, in order to obtain practical reflectance, the refractive index in reflection horizon is 0.0＜n＜1.0 and k＞2.0.

In addition, preferred pyroconductivity height.If with the high metal of above-mentioned reflectivity is example, can enumerate Ag (320W/MK), Cu (300W/MK), Au (230W/MK), Al (158W/MK) etc.

By using these metals or its alloy, can access the good medium of high-speed record.Even in the situation of recording wavelength short wavelengthization in future, by with above-mentioned metallic combination optimization, the possibility of good recording characteristic that obtains high reflectance and pyroconductivity simultaneously is also higher.

In addition, at the medium that organic dyestuff is used for recording layer, when writing down, the baseline of waveform is out-of-level to long mark (more than the 6T mark), and the tendency (below, be sometimes referred to as " waveform distortion ") of inclination is arranged.This waveform distortion becomes the reason of background wow and flutter deterioration sometimes.Although the background wow and flutter is good under low-speed record, the background wow and flutter under high-speed record is relatively poor, perhaps also has its reverse situation.The inventor thinks, the Temperature Distribution of the film thickness direction of described waveform distortion and recording layer has relation, can reduce described waveform distortion by combinatorial optimization with the heat conduction degree in combination, optical constant and the reflection horizon of the thickness in recording layer and reflection horizon, its result not only at 3.5m/s～35.0m/s but also in the line speed record scope of the such broad of 3.5m/s～about 70m/s, can carry out good record.

That is, according to above-mentioned reason, can not utilize the reflection horizon of record with laser lavishly on calorifics and optics owing to have, therefore in the line speed record scope of broad, it is good that the waveform of record mark can become.

In addition, above-mentioned " reflection horizon is a major component with copper, gold, aluminium " is meant that the reflection horizon is contained copper, gold or aluminium respectively separately, perhaps contains any two or more combination of copper, gold and the aluminium more than the 50 atom % altogether.For structure and optical characteristics optimization, preferably contain copper removal, gold element in addition with weatherability, film.As such element, can enumerate, for example, the group of forming by Al, Ag, Cr, Ni, Pt, Ta, Pd, Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, Ti, Zn, Zr and rare earth metal.The content of preferred these elements is 0.1 atom %～40 atom %.As the material that contains such element, for example, preferred CuAg, CuZrAg etc.

In addition, as illustrated in an embodiment, it is below 3 to the differential value dR/d λ (%/m) of wavelength that copper, gold and aluminium are in airborne reflectivity at wavelength 300nm～500nm.With respect to this, the maximal value of the differential value of the reflectivity of the fine silver in 300nm～500nm surpasses 5, the photostability of using from reality, this is not preferred, but, in the metallic reflective coating that for example contains silver, by reducing the ratio of components of silver, also can make dR/d λ value of the present invention is below 3.

As described above, is reflection horizon below 3 and the recording layer combination that contains the bad dyestuff of photostability by being in airborne reflectivity at wavelength 300nm～500nm to the differential value dR/d λ (%/nm) of wavelength, obtain following optical recording media thus first: it has the recording characteristic of hypervelocity such more than the 35m/s, has " reality is used " photostability that can be fit to use simultaneously.

As mentioned above, in order to form the reflection horizon of satisfying (dR/d λ)≤3 in the certain wavelengths scope of stipulating in the present invention, preferably the reflection horizon is contained be selected from least a element among Cu, Au and the Al, made the total ratio of above-mentioned element in above-mentioned reflection horizon reach 50 atom % simultaneously and (sometimes " atom % " is designated as " at% " by selected sputtering target.) more than.Among Cu, Au and Al, consider preferred Cu and Al at least from the reflectivity aspect.

According to the inventor's research as can be known, the island structure of the Al film of sputter might be grown in the temperature-rise period when hot and humid degree test or record, may reduce the flatness of film, and the result makes the wow and flutter of recording section descend sometimes.

Set out by the above fact, the reflection horizon is preferably the film of the Cu alloy that contains following composition (A) expression at least.

[forming (A)]

50at％≤Cu≤97at％

3at％≤Ag≤50at％

0.05at％≤X≤10at％

(at this, X represents to be selected from least a element in the group that Zn, Al, Pd, In, Sn, Cr, Ni form.In following record, sometimes this X is called " element kind ".But the total amount of Cu, Ag and X is below the 100at%.)

Specifically, in above-mentioned composition (A), the content of Cu is following scope: be generally more than the 50at%, be preferably more than the 65at%, more preferably more than the 80at%, and be generally below the 97at%, be preferably below the 95at%, more preferably below the 90at%.

In addition, in above-mentioned composition (A), the content of Ag is following scope: be generally more than the 3at%, be preferably more than the 5at%, and be generally below the 50at%, be preferably below the 30at%.

In order to form the reflection horizon of satisfying (dR/d λ)≤3 in the certain wavelengths scope of stipulating in the present invention, preferably the content with Ag is made as below the 50at%.In addition, embodiment described later confirms, in order to be recording layer with the organic dye layer that can be fit to the high-speed record that the present invention was put down in writing, by further guaranteeing effect that photostability is fully improved with the reflection horizon is combined, preferably the content with Ag is made as below the 30at% simultaneously.

In addition, in above-mentioned composition (A), the content of X is following scope: be generally more than the 0.05at%, be preferably more than the 0.1at%, and be generally below the 10at%, be preferably below the 5at%.In addition, select in the situation of metallic element as X more than 2 kinds, preferably its total satisfies above-mentioned scope.

Preferably the content with element kind X is made as more than the 0.05at%.In order to be easy to stably obtain effect of sufficient, more preferably more than the 0.1at%.Particularly,, when therefore target being carried out sputter, can think, understand some amount, therefore, preferably X is made as more than the 0.1at% as more stable composition not by the situation of sputter because the fusing point of Zn is low.

In addition, preferably the content of element kind X is made as below the 10at%.As long as it is below the 10at%, just guarantee high reflectance easily.In order to be easy to guarantee fully high reflectivity, more preferably the content with element kind X is made as below the 5at%.

In addition, can think that element kind X is to (dR/d λ) almost not influence.That is, with its for photostability of the present invention improves effect preferred element kind X, not as preferred element kind X in order to ensure the storage stability in the fine setting of reflectivity or reflection horizon.

Among the above-mentioned element kind X, more preferably Zn, Al, Pd, In, Sn.Since be easy to guarantee enough reflectivity, therefore, preferred especially Zn, Al, Pd.Particularly, according to the inventor's research as can be known,, has the possibility that can obtain higher reflectivity sometimes even the addition of Zn is less.In and Sn are also identical with Zn, Al, Pd, can expect above-mentioned effect.Particularly, the O of Zn, In, Sn and corrosion Cu alloy ₂Composition forms electroconductive oxide ZnO, In ₂O ₃, SnO ₂This electroconductive oxide ZnO, In ₂O ₃, SnO ₂Be the n N-type semiconductor N, and produce contact potential difference with Cu.Its result can think, oxonium ion (O ^2-) be easier to be pulled to Zn, In, Sn side than Cu, thus the oxidation of Cu postponed.

In addition,, use in the situation of low melting point and lower boiling element as element kind X, for form (manufacturing) as above high reflectance and contain the film (reflection horizon) of the Cu alloy of excellent storage stability at least, preferably use following sputtering target.

For example,, select in the situation of Zn (419.6 ℃ of fusing points, 907 ℃ of boiling points), preferably in sputtering target, comprise Zn about 0.01at%～2.5at% more than above-mentioned composition (A) as element kind X.This is because low melting point and lower boiling element are volatile.Also have between target when making sputter and the substrate every method, but for more stably, do not have and obtain the reflection horizon be scheduled to lavishly, preferred especially sputtering target satisfies following composition (B) with respect to the more recent inhibition volatilization in other place.As forming shown in (B),, just be easy to make reflection horizon with composition (A) as long as the composition in reflection horizon and the composition of target are made as same or close scope.

[forming (B)]

50at％≤Cu≤97at％

3at％≤Ag≤50at％

0.05at％≤X≤10at％

(at this, X represents to be selected from least a kind of element in the group of being made up of Zn, Al, Pd, In, Sn, Cr, Ni, and wherein, the total amount of Cu, Ag and X is below the 100at%.)

At this, the scope of the preferred content of Cu, Ag and element kind X with as the composition in above-mentioned reflection horizon and identical the getting final product of composition (A) that illustrates.

In addition, except that Zn recited above, about the fusing point of X, Al is 660.4 ℃, and Pd is 1550 ℃, and Sn is 231.97 ℃, and In is 156.6 ℃ (with reference to " rock ripple physics and chemistry is learned dictionary " the 5th edition, rock ripple bookstore, 1998).

Among the above-mentioned X, preferred especially Zn, Al, Pd, In, Sn.

As mentioned above, the difference of the fusing point of above-mentioned sputtering target is less.Thereby, the making that can omit the foundry alloy that above-mentioned patent documentation 4 (international disclose WO2002/021524 pamphlet) put down in writing.That is, following operation is possible.That is, in the high frequency smelting furnace, Cu and Ag are packed in the crucible, carry out vacuum melting, after above-mentioned Cu and Ag are fully fused, add element kind X with predetermined ratio.In addition, in the high frequency smelting furnace, Cu, Ag and element kind X are packed in the crucible, carry out vacuum melting and get final product with predetermined ratio.At this moment, as element kind X, when adding Al, Cr, Ni, Pd, In, Sn, get final product with predetermined ratio interpolation with Cu, Ag.On the other hand, as element kind X, when adding Zn, preferably Cu and Ag are fully being fused the back interpolation.This is because if from beginning most to load the high Zn of vapor pressure, then has because of volatilization to cause forming the tendency that does not reach setting.

At this, the fluxing temperature in the stove is set at about 1100 ℃～about 1200 ℃, as the material of crucible, uses C, Al ₂O ₃, MgO or ZrO ₂Deng.Next, carry out the casting of liquation, fused mass is cooled off in mold, it is solidified, thereby produce ingot bar, take out this ingot bar, be cooled to normal temperature from mold to mold.Then, the topmost of ingot bar emitted oral area to cut off to remove, utilize compressor that ingot bar is rolled, thereby produce tabular alloy., above-mentioned tabular alloy wire cut into article shape thereafter, the front of abrasive article, thus finally produce the sputtering target of Cu alloy of the present invention.

In addition, the situation that must carry out the production process of above-mentioned foundry alloy is generally, and the fusing point that the fusing point of the fusing point of principal element (is Cu for above-mentioned sputtering target) and interpolation element differs such about hundreds of ℃ differs very high situation.Suppose in the situation of the Ti that in the liquation (about 1000 ℃) of principal element Cu, adds 1668 ℃ of fusing points, utilize solid diffusion to carry out alloying, but its speed to be slow, equably and productive rate to carry out alloying well be difficult.If the ratio of the amount of Cu and Ti was made as 1: 1, then because their mutual relationship, fusing point is 960 ℃.Therefore, can easily carry out alloying with the principal element liquation.But, even also exist fusing point to have big-difference also needn't carry out the situation of foundry alloyization very much.This situation is that Pd is as X.In the Ag of 1100 ℃ of melt temperatures, do not drop into Pd (1554 ℃ of fusing points) even do not carry out foundry alloyization,, therefore carry out alloying easily yet because rate of propagation is fast.

Above-described sputtering target is for providing the material in the reflection horizon of excellence as described later.Therefore, if only from using above-mentioned sputtering target the aspect, reflection horizon of film forming consider, then to the restriction especially of the organic dyestuff that recording layer contained of the optical recording media that uses this reflection horizon.As such organic dyestuff, can enumerate big ring-type azepine annulene based dye (phthalocyanine dye, naphthalene phthalocyanine dye, porphyrin dye etc.), polymethine based dye (cyanine dye, merocyanine dyes, the sour inner dye in side etc.), anthraquinone based dye, Azulene based dye, azo-metal chelate based dye, indoaniline metal based dye etc.Among these organic dyestuff,, then preferably use azo-metal chelate based dye or phthalocyanine based dye if consider various key elements such as throughput rate, performance, actual effect.As the preference of azo-metal chelate based dye, can enumerate the azo-metal chelate dye that the metallic ion by the azo-compound of the structure with afore mentioned rules and Ni, Zn constitutes.But, as mentioned above, by be used in combination the predetermined effect of above-mentioned reflection horizon performance with the recording layer that contains " dyestuff of photostability difference ".

Below, in recording layer and reflection horizon, provide preferred record and read the physical property of wavelength.In the laser wave strong point of implementing record, preferably, keep suitable reflectivity by the driving of record or the restriction of optical system.In addition, for for example DVD-R, the refractive index behind the general record (n) can descend, and therefore refractive index (n) height of the recording layer before the record absorbs less than a certain amount of, and this is normally in order to ensure the necessary condition of the sufficient signal amplitude behind the record.In addition, if the reflection horizon is thin, then transmitted light increases and the composition that signal does not have a contribution is increased, and thus for the reflection horizon, it is generally acknowledged that the above thickness of certain thickness is necessary.

Therefore, in recording layer, preferably, writing down and reading the refractive index (n at wavelength place _w) satisfy n _w〉=1.4, writing down and reading the attenuation coefficient (k at wavelength place _w) satisfy k _w≤ 0.3, the thickness (d in the groove _w) satisfied 0.05≤(n _wd _w/ λ)≤0.3.And the reflection horizon is not used as in the situation of semi-transparent film, for the reflection horizon, and preferred thickness (d _r) satisfy 50nm≤d _r≤ 250nm.n _wThe upper limit be generally 4.0.k _wLower limit be generally 0.01.

Because above-mentioned optical constant and thickness are satisfied in recording layer and reflection horizon, can be write down and be read the high reflectance of light wave strong point and the signal amplitude behind the sufficient record, carry out record in order to utilize to drive, described record and read the high reflectance of light wave strong point and fully the signal amplitude behind the record be necessary.

[II. embodiments of the present invention]

Below, with reference to the accompanying drawings, preferred implementation of the present invention is elaborated.

About the 1st optical recording media of the present invention, as long as on substrate, have above-mentioned recording layer and reflection horizon, formation to other just is not particularly limited, but constitute as preferred, can enumerate, constitute the formation that forms at the lamination reflection horizon on 1 plate base that constitutes representative shown in the formation in clamping recording layer and reflection horizon between 2 plate bases and Fig. 1 (c) and recording layer of representative shown in Fig. 1 (a) and (b).In addition, the present invention is also applicable to the formation of the single-surface double-layer type shown in Fig. 2 (a) and (b).In addition, Fig. 1 (a)～(c) and Fig. 2 (a) and (b) are layer schematic sectional view that constitutes of the optical recording media of expression embodiment of the present invention.

Optical recording media 100 shown in Fig. 1 (a) has sequential laminating substrate (1) 101, recording layer (1) 102, reflection horizon (1) 103, protective finish (1) 104, tack coat 105, protective finish (2) 106, reflection horizon (2) 107, recording layer (2) 108 and substrate (2) 109 and the layer that obtains constitutes.Such optical recording media 100 constitutes in the following way: sequential laminating substrate (1) 101, recording layer (1) 102, reflection horizon (1) 103, protective finish (1) 104 and obtain fitting with dish 11; sequential laminating substrate (2) 109, recording layer (2) 108, reflection horizon (2) 107, protective finish (2) 106 and obtain fitting with dish 12; make protective finish (1) 104 and protective finish (2) 106 in opposite directions, utilize tack coat 105 to make applying use dish 12 to fit with dish 11 and applying.In addition,, in recording layer (1) 102, carry out recording of information and read, and, in recording layer (2) 108, carry out recording of information and read by from substrate (1) 101 side irradiating laser 111 by from substrate (2) 109 side irradiating lasers 110.

Optical recording media 200 shown in Fig. 1 (b) has sequential laminating substrate (1) 201, reflection horizon (1) 202, protective finish (1) 203, tack coat 204, protective finish (2) 205, reflection horizon (2) 206, recording layer 207 and substrate (2) 208 and the layer that obtains constitutes.Such optical recording media 200 constitutes in the following way: sequential laminating substrate (1) 201, reflection horizon (1) 202, protective finish (1) 203 and obtain virtual disk 21; sequential laminating substrate (2) 208, recording layer 207, reflection horizon (2) 206, protective finish (2) 205 and obtain fitting with dish 22; make protective finish (1) 203 and protective finish (2) 205 in opposite directions, utilize tack coat 204 to make virtual disk 21 and fit to use and coil 22 applyings.So,, carry out recording of information and read at recording layer 207 by from substrate (2) 208 side irradiating lasers 210.

Optical recording media 300 shown in Fig. 1 (c) has sequential laminating substrate 301, reflection horizon 302, recording layer 303, barrier layer 304 and transparent resin layer 305 and the layer that obtains constitutes.In this optical recording media 300,, on recording layer 303, carry out recording of information thus and read (face incident type) not from substrate 301 sides and from transparent resin layer 305 side irradiating lasers 310.

Optical recording media 400 shown in Fig. 2 (a) has sequential laminating substrate (1) 401, recording layer (1) 402, reflection horizon (1) 403, middle layer 404, recording layer (2) 405, reflection horizon (2) 406, tack coat 407 and substrate (2) 408 and the layer that obtains constitutes.In addition, the optical recording media 500 shown in Fig. 2 (b) has sequential laminating substrate (1) 501, recording layer (1) 502, reflection horizon (1) 503, tack coat (middle layer) 504, barrier layer 508, recording layer (2) 505, reflection horizon (2) 506 and substrate (2) 507 and the layer that obtains constitutes.In described optical recording media 400,500, by from substrate (1) 401,501 side irradiating lasers 410,510, in recording layer (1) 402,502 and recording layer (2) 405,505, carry out recording of information and read.

In addition, recording layer (1) 502 and recording layer (2) 505 as the optical recording media 500 shown in the recording layer (1) 402 of the recording layer 303 of the recording layer 207 of the optical recording media 200 shown in the recording layer (1) 102 of the optical recording media 100 shown in Fig. 1 (a) and recording layer (2) 108, Fig. 1 (b), the optical recording media 300 shown in Fig. 1 (c), the optical recording media 400 shown in Fig. 2 (a) and recording layer (2) 405, Fig. 2 (b) can be suitable for above-mentioned recording layer of the present invention.In addition, with these recording layer combinations, thereby reflection horizon (1) 503 and reflection horizon (2) 506 as the optical recording media 500 shown in the reflection horizon (1) 403 of the reflection horizon 302 of the optical recording media 300 shown in the reflection horizon (1) 202 of the optical recording media 200 shown in the reflection horizon (1) 103 of the optical recording media 100 shown in Fig. 1 (a) and reflection horizon (2) 107, Fig. 1 (b) and reflection horizon (2) 206, Fig. 1 (c), the optical recording media 400 shown in Fig. 2 (a) and reflection horizon (2) 406, Fig. 2 (b) can be suitable for above-mentioned reflection horizon of the present invention.

In addition, also can add various distortion in the formation of the optical recording media 400,500 of the optical recording media 100,200,300 of Fig. 1 (a)～(c) and Fig. 2 (a) and (b).For example, in the scope that does not break away from main points of the present invention, except that each above-mentioned layer, other layers can also be set, perhaps clipped layer perhaps changes the lamination order of each layer.As concrete example, in the optical recording media 200 of Fig. 1 (b), also can be following formation: omit reflection horizon (1) 202 and protective finish (1) 203, utilize tack coat 204 directly substrate 201 to be fitted to and fit with dish 22.In addition, in the optical recording media 100,200 of Fig. 1 (a) and (b), protective finish (1) 104,203 and protective finish (2) 106,205 are not set, as an alternative, use the tack coat 105,204 of function to bond with protective finish.

In addition, as other variation, also can for surface protection or prevent dirt etc. adhere to and the mirrored sides of substrate with ultraviolet curable resin layer or inorganic be film forming such as film.In addition, can not that record and the side of reading the plane of incidence of light are provided with the layer of undertaking the printing of also, the described layer of undertaking the printing of can be write (printing) to various printing machines such as ink-jet, sensible heat transfer printing or various writing appliance.

As the material of the substrate in the optical recording media of embodiments of the present invention, on the thickness direction of recording layer, basically in recording light with read that the light wavelength place is transparent to get final product.

Material as having so transparent thickness part can use the material that is made of resins such as for example acrylic resin, methacrylic resin, polycarbonate resin, polyolefin resin (particularly amorphous polyolefin), polyester resin, polystyrene resin, epoxy resin; The material that constitutes by glass; At material that is provided with the resin bed that constitutes by light-cured resin isoradial curable resin on glass etc.

In addition, consider preferred injection moulding polycarbonate from aspects such as high productivity, cost, anti-hydroscopicity.Consider preferred amorphous polyolefin from aspects such as chemical reagent resistance, anti-hydroscopicity.In addition, consider the preferred glass substrate from aspects such as high-speed responses.

In abutting connection with recording layer resin substrate or resin bed are set, and on this resin substrate or resin bed, can have gathering sill or the pit that writes down and read light.Preferred such gathering sill or pit produces when molding substrate, but also can use ultraviolet curable resin layer to produce on substrate.At gathering sill is in the spiral helicine situation, and preferably this separation is about 0.1 μ m～about 2.0 μ m.

According to AFM (atomic force microscope) measured value, groove depth is generally more than the 50nm.As DVD-R, for red semiconductor laser, groove depth is generally more than the 100nm, but particularly, for from 1 times of speed of low speed (below, be designated as " 1 * " sometimes.) at a high speed 8 * the scope of writing speed in can record, groove depth is more than the 120nm.In addition, groove depth is generally below the 200nm, is preferably below the 180nm.In the situation of groove depth greater than above-mentioned lower limit, under low speed, easily produce degree of modulation, in the situation of groove depth, easily guarantee enough reflectivity less than above-mentioned higher limit.According to AFM (atomic force microscope) measured value, groove width is generally more than the 0.10 μ m, is preferably more than the 0.20 μ m.In addition, groove width is preferably below the 0.40 μ m.In addition, as DVD-R, for the high-speed record purposes of utilizing red semiconductor laser, more preferably groove width is made as 0.28 μ m～0.34 μ m.In the situation of groove width, easily obtain the push-pull signal amplitude fully greater than above-mentioned lower limit.In addition, substrate deformation is bigger to the influence of tracer signal amplitude.Therefore, as long as make groove width greater than above-mentioned lower limit, 8 * situation about writing down under the above high speed in, just suppress the influence that heat is interfered easily, and the good wow and flutter that is easy to get.In addition, recording power nargin broadens, and the allowable value of the change of laser power is become big etc., and recording characteristic or record condition improve.In the situation of groove width less than above-mentioned higher limit, 1 * waiting in the low-speed record, the heat that can suppress in the record mark is interfered, and can obtain good quiver value easily.

Can recording address information in the optical recording media of embodiments of the present invention, the information such as kinds of information, recording impulse condition and optimal recording power of medium.As the form of these information of record, for example, LPP (Land Pre-Pit) that the normative document of use DVD-R, DVD+R is put down in writing or the form of ADIP (Address in Pre-groove) etc. get final product.

About the ratio of the material of recording layer, mixing and thickness as mentioned above.In addition, between groove the thickness of portion preferably less than the thickness in the groove.

As the film build method of recording layer, can enumerate vacuum deposition method, sputtering method, scrape the skill in using a kitchen knife in cookery, film forming methods commonly used such as casting, spin-coating method, infusion process, but consider preferred spin-coating method from mass productivity, cost aspect.In addition, consider from obtaining aspects such as the uniform recording layer of thickness, with respect to rubbing method, preferred vacuum deposition method.

Utilize in the situation of spin-coating method film forming, preferred rotating speed is 10rpm～15000rpm, after the spin coating, heats or is exposed to processing such as solvent vapour.

Scrape coating processes such as the skill in using a kitchen knife in cookery, casting, spin-coating method, infusion process as utilization and form the coating solvent of the situation of recording layer, do not get final product, be not particularly limited so long as do not damage the solvent of substrate.Can enumerate, for example, diacetone alcohol, 3-hydroxy-3-methyl-ketols solvents such as 2-butanone; Cellosolve such as methyl cellosolve, ethyl cellosolve kind solvent; Chain such as normal hexane, normal octane varsol; Cyclic hydrocarbon kind solvents such as cyclohexane, methylcyclohexane, ethyl cyclohexane, dimethyl cyclohexane, n-butyl cyclohexane, tert-butyl group cyclohexane, cyclooctane; Tetrafluoropropanol, octafluoro are for perfluoroalkyl alcohols solvents such as amylalcohol, hexafluoro butanols; Hydroxycarboxylic acid esters solvents such as methyl lactate, ethyl lactate, 2-hydroxy-methyl isobutyl acid etc.

In the situation of vacuum deposition method, the recording layer composition of for example organic dyestuff and various adjuvants in case of necessity etc. packed into is arranged on crucible in the vacuum tank, utilizes suitable vacuum pump to be vented to about 10 in the vacuum tank ^-2Pa～about 10 ^-5Behind the Pa, the heating crucible, thereby make recording layer composition evaporation, and make this composition evaporation to relative with crucible on the substrate that is provided with, form recording layer thus.

Be used for the stable recording layer or improve the sunproof compound except that above-mentioned, recording layer can also and be used following dyestuff, thereby make the optical recording media that writes down corresponding to by the laser in the wavelength coverage more than 2, described dyestuff is suitable for using the record of the recording light of the red laser of the used about 620～about 690nm of wavelength of the about 770nm of the used wavelength of common CD-R～near-infrared laser of about 830nm, DVD-R or 2 above wavelength such as so-called blue laser such as wavelength 410nm or 515nm respectively.

As can and the dyestuff of usefulness, can enumerate the following dyestuff with the azo-metal chelate dye identical systems with above-mentioned specific characteristic or structure: azo based dye or azo are metal chelate dye, the cyanine based dye, the sour inner salt based dye in side, the naphthoquinones based dye, the anthraquinone based dye, the porphyrin based dye, テトラピラ Port Le Off イラジ Application, the indophenols based dye, the pyralium salt based dye, thiapyran inner salt based dye, the Azulene based dye, the triphenylmethane based dye, the xanthene based dye, the indanthrene based dye, indigo based dye, the thioindigo based dye, the merocyanine based dye, two pyrroles's methylene based dyes, the thiazine based dye, acridine system dye oxazine based dye, indoaniline based dye etc., and also can be the dyestuff of other system.In addition, as the thermal decomposition promoter of dyestuff, can enumerate, for example, metal is that octane promoter, metallocene compound, diacetone are metallic compounds such as metal complex.

Further, in recording layer of the present invention, can also as required and use bonding agent, levelling agent, defoamer etc.As preferred adhesive, can enumerate polyvinyl alcohol (PVA), polyvinyl pyrrolidone, NC Nitroncellulose, cellulose acetate, ketone resins, acrylic resin, polystyrene resins, polyurethanes resin, polyvinyl butyral, polycarbonate, polyolefin etc.

The material in reflection horizon and composition are as mentioned above.

As the method that forms the reflection horizon, can enumerate sputtering method, ion plating, chemical vapor deposition method, vacuum deposition method etc.

Consider that from aspects such as recording characteristic or commercial production the thickness in reflection horizon is made as following scope.That is, the thickness in reflection horizon is generally more than the 50nm, is preferably more than the 60nm, on the other hand, is generally below the 300nm, is preferably below the 250nm, more preferably below the 200nm.

In addition, consider that the film of the roughness (particle diameter) of the film in preferred reflection horizon and gold quite or little of the degree that is lower than golden film from weatherability or reflectivity aspect.Particularly, when writing down and reading the high density recording of light wave length, in the situation of aluminium, its roughness is variable big, and therefore the method for utilizing alloying that its flatness is improved is necessary.In addition, for the roughness of the film that reduces the reflection horizon, can also enumerate argon when making sputter and press and method such as reduce.

As the material that is formed on the protective seam on the reflection horizon,, be not particularly limited so long as the protection reflection horizon is not got final product by the material of outside destroy.As the material of organic substance, can enumerate thermoplastic resin, thermoset resin, electronics line curable resin, UV (ultraviolet ray) curable resin etc.In addition, as dead matter, can enumerate SiO ₂, SiN ₄, MgF ₂, SnO ₂Deng.

For thermoplastic resin, thermoset resin etc., can coating fluid be coated with by being dissolved in appropriate solvent, and carry out drying, form thus.For the UV curable resin, directly or be dissolved in appropriate solvent, thereby after preparing coating fluid, be coated with this coating fluid, and irradiation UV light, thereby make its curing, form thus.As the UV curable resin, can use, for example, acrylic resins such as ammonia ester acrylate, epoxy acrylate, polyester acrylate.These materials can be used alone or as a mixture, also can be not only 1 layer and make multilayer film and use.

As the formation method of protective seam, can use in the same manner such as methods such as rubbing methods such as spin-coating method or casting, sputtering method or chemical vapor deposition methods with recording layer, but wherein preferred especially spin-coating method.

The thickness of preferred protective seam is generally more than the 0.1 μ m, is preferably more than the 3 μ m.On the other hand, the thickness of protective seam is generally below the 100 μ m, is preferably below the 30 μ m.

The laser that is used to write down and read is not particularly limited, yet can enumerate, for example, in the relative broad range of visibility region, can select near the high output semiconductor laser the dye laser of wavelength, the He-Ne Lasers of wavelength 633nm, the wavelength 680nm, the 660nm that are being developed recently, 650nm, the 635nm, the higher harmonics conversion YAG laser of wavelength 532nm, near the blue semiconductor laser the 405nm etc.From aspects such as in light weight, processing easiness, miniaturization, cost, especially preferred semiconductor laser.At a wavelength or 2 above wavelength of selecting among these, the optical recording media of embodiments of the present invention can carry out high density recording and read.

Usually focus on laser about 1 μ m by recording layer irradiation, come thus the optical recording media of embodiment of the present invention is carried out record the two sides that is arranged on substrate or single face.The recording layer of laser radiation part absorbs laser energy and causes heating up, the thermal distortion of recording layers such as the result decomposes, heat release, fusion, and optical characteristics such as phasic difference or optical constant change.

Read the laser of usefulness by irradiation, read reflectivity poor of part that optical characteristics changes and the part that does not change, the reading of the information that is recorded thus.

[III. key concept 2 of the present invention]

In addition, the azo-metal chelate dye that is made of the metallic ion of the azo based compound of above-mentioned general formula (1) expression and Zn is not limited to above-mentioned [I. key concept 1 of the present invention] described optical recording media (the 1st optical recording media of the present invention), in following optical recording media, above-mentioned dyestuff can be widely used as the organic dyestuff of above-mentioned recording layer: described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is perhaps carried out record with the line speed record more than the 35.0m/s less than 0.4 μ m.

Promptly, other optical recording media of the present invention is following optical recording media: described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is perhaps carried out record with the line speed record more than the 35.0m/s less than 0.4 μ m; The organic dyestuff of above-mentioned recording layer is the azo-metal chelate dye that constitutes of the metallic ion by the azo based compound of above-mentioned general formula (1) expression and Zn (below, be referred to as " the 2nd optical recording media of the present invention " sometimes).Utilize the 2nd optical recording media of the present invention, can obtain endurance life characteristic particularly (long preservation stability and hot and humid following storage stability) the such advantage of excellence.

In addition, in the 2nd optical recording media of the present invention, the content that illustrates in the details of the details of the azo based compound of above-mentioned general formula (1) expression or concrete example and the azo-metal chelate dye that is made of described azo based compound and Zn metallic ion or concrete example and above-mentioned [I. key concept 1 of the present invention] joint is identical.

In addition, even in the 2nd optical recording media of the present invention, also the material of above-mentioned composition (A) expression is contained in the reflection horizon of the preferred described optical recording media that constitutes.Utilize the optical recording media that constitutes like this, the reduction of reflectivity can be suppressed to minimum, and can obtain the advantage of endurance life characteristic excellence.

In addition, in the 2nd optical recording media of the present invention, the details of above-mentioned composition (A) or concrete example are also identical with the content of explanation in above-mentioned [I. key concept 1 of the present invention] joint.

[IV. key concept 3 of the present invention]

In addition, at least the sputtering target that has the material that above-mentioned composition B represents also is not limited to the formation in the reflection horizon of above-mentioned [I. key concept 1 of the present invention] described optical recording media (the 1st optical recording media of the present invention), in following optical recording media, above-mentioned sputtering target can be extensive use of when forming above-mentioned reflection horizon: described optical recording media has on the substrate of concentric circles or spiral helicine groove and has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal.

That is sputtering target of the present invention employed sputtering target when forming above-mentioned reflection horizon in following optical recording media: described optical recording media has on the substrate of concentric circles or spiral helicine groove and has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal; And sputtering target of the present invention is the target of the material that has above-mentioned composition B at least and represent.Utilize sputtering target of the present invention, can be with the minimum that is reduced to of reflectivity, and the high-quality medium of endurance life characteristic excellence can be provided, in addition, also having can the low-cost advantage of making.

In addition, in the sputtering target of the present invention, the details of above-mentioned composition B or concrete example are identical with the content of explanation in above-mentioned [I. key concept 1 of the present invention] joint.

In addition, sputtering target of the present invention can be specially adapted to the formation in the reflection horizon of following optical recording media, in the described optical recording media, described organic dyestuff is the azo-metal chelate dye by the metallic ion formation of the azo based compound of above-mentioned general formula (1) expression and Ni, Zn.By sputtering target of the present invention being used for the formation in the reflection horizon of such optical recording media, can obtain under the situation that changes existing manufacturing process hardly, can making at low cost the advantage of medium.

[V. key concept 4 of the present invention]

In addition, the azo-metal chelate dye that is made of the metallic ion of the azo based compound of above-mentioned general formula (1) expression and Zn can be widely used as the organic dyestuff of following optical recording media: described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is perhaps carried out record with the line speed record more than the 35.0m/s less than 0.4 μ m.

Below, the azo-metal chelate dye that will be made of the metallic ion of the azo based compound of above-mentioned general formula (1) expression and Zn is called " dyestuff of the present invention ".By dyestuff of the present invention being used for the optical recording media of above-mentioned high-speed record or high density recording, compared with the prior art, can obtain following advantage: the record nargin that can reach low wow and flutter, low error rate and broad.

In addition, the content that illustrates in the details of the details of the azo based compound of above-mentioned general formula (1) expression that has of dyestuff of the present invention or concrete example and dyestuff of the present invention or concrete example and above-mentioned [I. key concept 1 of the present invention] joint is identical.

Embodiment

Below, the present invention will be described in more detail by embodiment, but the present invention is only otherwise exceed its main points, is not limited to following examples.

[determination method of individual layer dyestuff conservation rate]

In following each embodiment and comparative example, short of special declaration is measured the dyestuff conservation rate in the following order.

At first, be ready to implement the substrate of the polycarbonate manufacturing of mirror finish.Use is as the tetrafluoropropanol of the concentration 1.4 weight % of the dye mixture of determination object (below, be called " TFP ") solution, according to following each embodiment and comparative example in make the identical mode of dye coating, implement spin coating.Cut the small pieces of resulting dyestuff individual layer, use spectrophotometer (UV-VIS) to carry out the mensuration of the wavelength dispersion of absorbance.Maximal value with resulting absorbance is an initial value.

Next, the サ Application テスト XLS+ that uses light fastness test machine (East Yang Jing Machine to make), measure the integrated exposure that satisfies 5 grades of Wool scale, and means for correcting.The illumination of this exposure intensity is mapped on the small pieces of above-mentioned dyestuff individual layer, utilizes the wavelength dispersion of spectrophotometric determination absorbance once more.Ratio with the maximal value of the absorbance that obtains at this and above-mentioned initial value is the dyestuff conservation rate.In following each embodiment and comparative example, with activity 550W/m ²The xenon lamp of irradiation 2200W 40 hours, this is to satisfy imposing a condition of 5 grades of Wool scale.

[determination method of reflectivity]

In following each embodiment and comparative example, only otherwise special declaration, the mensuration of the airborne reflectivity in reflection horizon is carried out in the following order.That is, use material with the reflection horizon to be splashed on the microslide and the sample that obtains, from face irradiation measuring reflectance light (device: the U3010 of Hitachi type spectrophotometer; Mode determination: reflection measurement pattern; Sweep velocity: 300nm/min; Slit: 1nm).Utilize the measured value of resulting reflectivity, calculate dR/d λ, try to achieve its maximal value dR/d λ (max) wavelength X=300nm～500nm.

[embodiment 1]

Utilize spin-coating method, on the support substrate that the polycarbonate of the thickness 0.6mm of the gathering sill with track space 0.74 μ m, groove width 320nm, groove depth 160nm is made, be provided with by 40 weight % dyestuff A (azo-metal chelate dye that constitutes by azo based compound shown in 2 following structural formula (a) and nickel) and 60 weight % dyestuff B (by azo based compound shown in 2 following structural formula (b) and zinc (divalent ion: Zn ²⁺) azo-metal chelate dye that constitutes) recording layer (thickness 50 nm in the groove) that constitutes, and recording layer to be reached demonstrate absorbance (Optical Density: with the air is that reference is measured the absorbance at wavelength 598nm place that obtains) be 0.65 thickness.In addition, coating solution is the TFP solution of concentration 1.3 weight %, and the rotating speed of spin coating is 1000rpm～2500rpm.Next, utilize sputtering method, copper (Cu) is deposited on the recording layer, and form the Cu reflection horizon of the thickness of 120nm.Compare with the membrance casting condition in well-known reflection horizon, the argon during sputter is pressed less, improves power input.Further, spin coating uv curing resin on this reflection horizon (Nippon Kayaku K. K makes KAYARAD SPC-920) also solidifies it, thereby forms the protective seam of 10 μ m.Be ready to 2 laminates that obtain like this, use UV curing type cementing agent (SK7100 that ソニ one ケミカ Le is made), 2 described laminates are fitted, make substrate outside, produce optical recording media thus.

In addition, the dyestuff conservation rate of dyestuff A and dyestuff B dyestuff single coating film separately is respectively 90.4% and 0%, and the dyestuff conservation rate of recording layer individual layer is 56%.

In addition, utilize above-mentioned method, measure the reflectivity of Cu reflection horizon individual layer and the value of dR/d λ.Its result is shown in respectively in the curve map of Fig. 8 and Fig. 9 (a).The reflectivity of the 300nm～500nm of Cu reflection horizon individual layer is 29%～56% (Fig. 8).In addition, the value of the dR/d λ (max) in the co-wavelength scope is 0.36 (Fig. 9 (a)).

Adopt the record and the reading device of wavelength 650nm, hole count 0.65, use is based on the recording impulse policy condition of DVD-RSpecification for General Ver.2.1 or DVD+R Specification Ver.1.20, under writing speed 56.0m/s (16 times of speed of DVD-R), resulting optical recording media is carried out the random signal record that the shortest mark length is the 8-16 modulation (EFMplus modulation) of 0.4 μ m.In addition, the radiation pulses of the long recording laser of 3T mark is wide is 6.5ns.In addition, use identical evaluation machine to come the signal of the part of reading and recording formation, and measure nargin (the recording power nargin of wow and flutter and the asymmetry nargin of wow and flutter).In addition, about being used for the record of " reality is used " sunproof evaluation (the recording characteristic evaluation behind the xenon lamp pre-irradiation), carry out 8 times of speed recordings, and utilize DVD-ROM inspection machine (the LM2 20A that the シバソ of Co., Ltd. Network is made), measure minimum value (the best jitter characteristics value of the wow and flutter (data to clock jitter) of its recording section.Below, be called " background wow and flutter ") and the maximal value of PI (Parity ofInner-code) mistake (below, be called " PI max ").

The measurement result of recording power nargin is shown in the curve map of Fig. 4 (a), and the measurement result of asymmetry nargin is shown in the curve map of Fig. 4 (b).Shown in Fig. 4 (a) and (b) like that, using the optical recording media background wow and flutter of the present embodiment in Cu reflection horizon is 7%, very good.In addition, the asymmetry nargin that wow and flutter reaches below 9% is about 18%, and the asymmetry nargin that wow and flutter reaches below 8% is more than 10%, though asymmetry near 5%, wow and flutter is about 8%, and is also very good.

In addition, the measurement result before and after the light fastness test of background wow and flutter is shown in the curve map of Fig. 4 (c), and the measurement result of PI max is shown in the curve map of Fig. 4 (d).By Fig. 4 (c), (d) as can be known, optical recording media about the present embodiment that uses the Cu reflection horizon, even the xenon lamp irradiation time is 40 hours (5 grades of Wool scale), the background wow and flutter also only increases a little, but PI max does not increase fully, compare with the situation in Ag described later reflection horizon, " reality is used " photostability is greatly improved.

[embodiment 2]

In embodiment 1, the material that removes the reflection horizon becomes gold (Au), and its thickness is become beyond the 90nm, produces optical recording media with process similarly to Example 1.To resulting optical recording media, implement record and read background wow and flutter and PI max before and after the mensuration light fastness test with condition similarly to Example 1.

The measurement result of background wow and flutter is shown in the curve map of Fig. 4 (c), and the measurement result of PI max is shown in the curve map of Fig. 4 (d).By Fig. 4 (c), (d) as seen, for the optical recording media of the present embodiment that uses the Au reflection horizon, compare with the situation in Cu reflection horizon, its effect has some deteriorations, but can obtain good result.

In addition, utilize above-mentioned method, measure the reflectivity of Au reflection horizon individual layer and the value of dR/d λ.Its result is shown in the curve map of Fig. 8 and Fig. 9 (b) respectively.The reflectivity of the 300nm～500nm of Au reflection horizon individual layer is 37%～50% (Fig. 8).In addition, the value of the dR/d λ (max) in the co-wavelength scope is 0.72 (Fig. 9 (b)).

[comparative example 1]

In embodiment 1, the material that removes the reflection horizon becomes silver (Ag), and its thickness becomes beyond the 120nm, produces optical recording media with process similarly to Example 1.To resulting optical recording media, implement record and read background wow and flutter and PI max before and after mensuration nargin (recording power nargin and asymmetry nargin), the light fastness test with condition similarly to Example 1.

The measurement result of recording power nargin is shown in the curve map of Fig. 4 (a), and the measurement result of asymmetry nargin is shown in the curve map of Fig. 4 (b).By Fig. 4 (a) and (b) as can be known, for the optical recording media of this comparative example that uses the Ag reflection horizon, compare with the situation in Cu reflection horizon, the background wow and flutter is relatively poor, and the nargin of asymmetry is also narrow in addition.

In addition, the measurement result of background wow and flutter is shown in the curve map of Fig. 4 (c), and the measurement result of PI max is shown in the curve map of Fig. 4 (d).By Fig. 4 (c), (d) as can be known, optical recording media for this comparative example that uses the Ag reflection horizon, in the condition (xenon lamp irradiation 40 hours) of 5 grades of Wool scale, background wow and flutter, mistake (PI max) all worsen, for the Ag reflection horizon, can not bear 5 grades of conditions of Wool scale, that is, " reality is used " photostability is relatively poor.In addition, put down in writing in the standard of DVD-R, being no more than 280 with wrong (PI max) is necessary condition.

In addition, utilize above-mentioned method to measure the reflectivity of Ag reflection horizon individual layer and the value of dR/d λ.Its result is shown in the curve map of Fig. 8 and Fig. 9 (c) respectively.The reflectivity of the 300nm～500nm of Ag reflection horizon individual layer is 4%～96% (Fig. 8).In addition, the value of the dR/d λ (max) in the co-wavelength scope is 5.6 (Fig. 9 (c)).

[embodiment 3]

In embodiment 1, (Ni is divalent ion: Ni except that the Ni complex compound dyestuff C (65 weight %) that dyestuff A is become the azo based compound shown in 2 following structural formula of coordination (c) ²⁺), dyestuff B becomes the cyanine based dye D shown in the following structural formula (d) (35 weight %) and in addition, produces optical recording media with process similarly to Example 1.In addition, resolve, confirm that the interior thickness of groove of recording layer is 25nm by the section that utilizes electron microscope.In addition, the thickness in Cu reflection horizon is 120nm, and is identical with embodiment 1.To this optical recording media, implement record and read background wow and flutter and PI max before and after mensuration nargin (recording power nargin and asymmetry nargin), the light fastness test with condition similarly to Example 1.

In addition, the dyestuff conservation rate of the dyestuff single coating film separately of dyestuff C and dyestuff D is respectively 97.0% and 0%, and the dyestuff conservation rate of recording layer individual layer is 68.2%.

The measurement result of recording power nargin is shown in the curve map of Fig. 5 (a), and the measurement result of asymmetry nargin is shown in the curve map of Fig. 5 (b).By Fig. 5 (a) and (b) as can be known, for the optical recording media of the present embodiment that uses the Cu reflection horizon, wow and flutter is that the power margin below 9% is about 10mw, has realized extremely stable power margin.In addition, even asymmetry surpasses+6.0%, also have the wow and flutter below 9%, the asymmetry nargin that demonstrates the wow and flutter below 9% is the nargin of about 20% non-like this constant width.Mean that the hot deterioration of record mark (accumulation of heat and heat are interfered) is also very little the noting of the such hypervelocity of 56m/s (16 times of speed) even described nargin is fabulous.

In addition, the measurement result of background wow and flutter is shown in the curve map of Fig. 5 (c), and the measurement result of PI max is shown in the curve map of Fig. 5 (d).Shown in Fig. 5 (c), (d), for the optical recording media of the present embodiment that uses the Cu reflection horizon, to compare with the situation in Ag described later reflection horizon, " reality is used " photostability improves greatly.In addition, for the dyestuff individual layer, be 0% the photostability dyestuff D of deterioration greatly though contain the dyestuff conservation rate, can realize having " on actual the use " sunproof CD of 5 grades of Wool scale.

[comparative example 2]

In embodiment 3, the material that removes the reflection horizon becomes silver by copper, is provided with beyond the Ag reflection horizon of thickness 120nm, produces optical recording media with process similarly to Example 3.To this optical recording media, implement record, read with condition similarly to Example 1, measure the background wow and flutter and the PI max of nargin (recording power nargin and asymmetry nargin), light fastness test front and back.

The measurement result of recording power nargin is shown in the curve map of Fig. 5 (a), and the measurement result of asymmetry nargin is shown in the curve map of Fig. 5 (b).Shown in Fig. 5 (a), for the optical recording media of this comparative example that uses the Ag reflection horizon, to compare with the situation in Cu reflection horizon, recording power nargin is very narrow.

In addition, the measurement result of background wow and flutter is shown in the curve map of Fig. 5 (c), and the measurement result of PI max is shown in the curve map of Fig. 5 (d).For the optical recording media of this comparative example that uses the Ag reflection horizon, in Fig. 5 (c), the background wow and flutter after 40 hours worsens, and in Fig. 5 (d), mistake (PI max) is far above 280.Hence one can see that, uses the optical recording media of this comparative example in Ag reflection horizon can not bear 5 grades of Wool scale.

[embodiment 4]

Remove writing speed is become 35.0m/s (be equivalent to 10 *), become beyond the 7.9ns the radiation pulses of the long recording laser of 3T mark is wide, optical recording media to embodiment 3, implement to write down and read with condition similarly to Example 1, and measure nargin (recording power nargin and asymmetry nargin).

With mark " ● " measurement result of recording power nargin is shown in the curve map of Fig. 6 (a) respectively, the measurement result of asymmetry nargin is shown in the curve map of Fig. 6 (b).According to Fig. 6 (a) as can be known, identical with the situation of 56.0m/s record even in the present embodiment that writes down with 35.0m/s, background wow and flutter 6.0% (very good record) also is possible.

[comparative example 3]

Remove writing speed is become 35.0m/s (be equivalent to 10 *), wide the becoming beyond the 7.9ns of radiation pulses of the long recording laser of 3T mark, optical recording media to comparative example 2, implement to write down and read with condition similarly to Example 1, and measure nargin (recording power nargin and asymmetry nargin).

All with mark " ▲ " measurement result of recording power nargin is shown in the curve map of Fig. 6 (a), the measurement result of asymmetry nargin is shown in the curve map of Fig. 6 (b).According to Fig. 6 (a) and (b) as can be known, background wow and flutter 6.7%, relatively better, but compare with the optical recording media of the use Cu reflectance coating of embodiment 4, power margin deterioration relatively then.

[comparative example 4]

In embodiment 1, (Ni is divalent ion: Ni to remove " photostability is good " Ni complex compound dyestuff E that will " photostability is relatively poor " dyestuff B becomes the azo based compound that 2 following structural formula of coordination (e) represent ²⁺), with dyestuff A and dyestuff E with 50 weight %: the ratio of 50 weight % mix use beyond, produce optical recording media with process similarly to Example 1.Thickness is 30nm in the groove of resulting records layer.In addition, the thickness in Cu reflection horizon is 120nm.

In addition, the dyestuff conservation rate of dyestuff E single coating film is 87.3%, and the dyestuff conservation rate of this recording layer individual layer is 89.0%.

To this optical recording media, implement record, read with condition similarly to Example 1, measure the background wow and flutter and the PImax of nargin (recording power nargin and asymmetry nargin), light fastness test front and back.

The measurement result of recording power nargin is shown in the curve map of Fig. 7 (a), and the measurement result of asymmetry nargin is shown in the curve map of Fig. 7 (b).By Fig. 7 (a) and (b) as can be known, even the Cu reflection horizon is made in the reflection horizon, also almost can't see the improvement of characteristic.The background wow and flutter is more than 9%, and power margin, asymmetry nargin are all extremely narrow.Particularly, asymmetry nargin worsens, even in-5% so quite low recording power, also can find hot deterioration, wow and flutter is deterioration also, surpasses the background wow and flutter more than 1%.In addition, in the situation of asymmetry nargin 5%, preferably making wow and flutter is below 9%.

In addition, the measurement result of background wow and flutter is shown in the curve map of Fig. 7 (c), and the measurement result of PI max is shown in the curve map of Fig. 7 (d).Shown in Fig. 7 (c), (d), " reality is used " photostability is very good.

In addition, reflection horizon on the above-mentioned recording layer is become in the situation in the Ag reflection horizon identical with comparative example 1, background wow and flutter in light fastness test becomes 7.0% from 6.9%, and the PI max in light fastness test becomes 8 from 5, demonstrates very good " on actual the use " photostability.

From above result as can be known, in the optical recording media of this comparative example that uses the recording layer only contain the good dyestuff of photostability, for the record of the such hypervelocity of 16 times of speed recordings, hot deterioration is bigger, does not form good record mark.The degree of this deterioration is bigger, even use for example Cu reflection horizon, also we can say to be difficult to improve.

[1 times of speed recording test]

For the optical recording media of the above embodiments 1, embodiment 3, comparative example 1, comparative example 2 and comparative example 4, except that writing speed being become 1 times of speed, implement record and read mensuration background wow and flutter with condition similarly to Example 1.The results are shown in following table 1.

Table 1

	Background wow and flutter (%) during 1 times of speed recording (3.5m/s)
		The optical recording media of embodiment 1	7.4
The optical recording media of comparative example 1	8.4	The optical recording media of embodiment 1	7.4
The optical recording media of comparative example 1	8.4	The optical recording media of embodiment 3	7.0
The optical recording media of comparative example 2	7.7	The optical recording media of embodiment 3	7.0
The optical recording media of comparative example 2	7.7	The optical recording media of comparative example 4	8.1

It is generally acknowledged that the background wow and flutter is necessary for below 9%.As shown in table 1, under 1 times of speed recording, the background wow and flutter of the optical recording media of embodiment 1, embodiment 3, comparative example 1, comparative example 2, comparative example 4 is below 9%, demonstrates good recording characteristic.However, under high-speed record, as above-mentioned the record, good and bad as can be seen.

From above result as can be known, the optical recording media that satisfies each embodiment of regulation of the present invention demonstrates good recording characteristic under the writing speed (1 times of speed, 10 times of speed, 16 times of speed) of non-constant width.

[embodiment 5]

Utilize above-mentioned method, measuring with aluminium (Al) is the reflectivity and the dR/d λ in the reflection horizon (Al reflection horizon individual layer) of material.Its result is shown in the curve map of Fig. 8 and Fig. 9 (d) respectively.By Fig. 9 (d) as can be known, in the scope of 300nm～500nm, the value of the dR/d λ of Al reflection horizon individual layer is always below 0.1.

[embodiment 6]

Identical with above-mentioned [determination method of reflectivity], with Cu87.2 atom %/Ag12.8 atom % (below, be designated as " CuAg in the time of suitably _12.8") and Cu86.4 atom %/Ag12.9 atom %/Pd0.7 atom % (below, be designated as " CuAg in the time of suitably _12.9Pd _0.7") be splashed to respectively on the other microslide, measure reflectivity from the face side.In addition, the condition of sputter is identical with embodiment 1.

Figure 10 is with CuAg _12.8And CuAg _12.9Pd _0.7The curve map that shows of the measurement result of the Ag, the Au that in [embodiment 5] etc., obtain of the measurement result of reflectivity, Cu.In Figure 10, transverse axis is represented wavelength X (nm), and the longitudinal axis is represented reflectivity (%).As shown in Figure 10, CuAg _12.8And CuAg _12.9Pd _0.7All have visibly different optical characteristics with Cu, compare with Cu, reflectivity is slightly near Ag.

In addition, calculate described CuAg _12.8And CuAg _12.9Pd _0.7DR/d λ.Figure 11 (a) and (b) are respectively and show CuAg _12.8And CuAg _12.9Pd _0.7The curve map of result of calculation of dR/d λ.By Figure 11 (a) and (b) as can be known, noise raises on the whole, but in the wavelength coverage (with reference to figure 9) of the 300nm～500nm of the peak wavelength of the maximal value 5.6 of the dR/d λ that has Ag, finds that the noise of dR/d λ has faint rising.

At this, utilize following formula, by the reflectivity R of the Ag of comparative example 1 _AgReflectivity R with the Cu of embodiment 1 _CuCalculate Cu _(1-X)Ag _XReflectivity R (Cu under each wavelength of (atom %:at%) _(1-X)Ag _X).

R(Cu _(1-X)Ag _X)＝{(1-X)/100}×R(Cu)+(X/100)×R(Ag)

Its result can obtain following spectrum, and described spectrum demonstrates the wavelength interdependence that blending ratio with Ag and Cu is made as the such reflectivity of Figure 10 in the situation arbitrarily.In addition, for predetermined Ag and the blending ratio of Cu, calculate dR/d λ in the same manner with Figure 11 (a), thereby try to achieve the maximal value of the dR/d λ in 300nm～500nm respectively.At this, be transverse axis with the content of Ag, be the longitudinal axis with the maximal value of the dR/d λ in the wavelength coverage of the 300nm～500nm that will try to achieve by said process, the curve map that mapping obtains is shown in Figure 12.As shown in the figure as can be known, the maximal value of the dR/d λ that sees in 300nm～500nm and Ag amount is relevant.In addition, by we can say with figure, it is situations that Ag reaches about 50 at% that dR/d λ reaches 3.

On the other hand, if by CuAg _12.8The measured value supposition of the maximal value (referring to Fig. 9 (c)) of the dR/d λ at 300nm～500nm place among the peaked measured value (referring to Fig. 9 (a)) of the dR/d λ at 300nm～500nm place and the Ag (100at%) among the peaked measured value (referring to Figure 11 (a)) of the dR/d λ at middle 300nm～500nm place, the Cu (100 at%), dR/d λ is 3 o'clock, and the Ag amount is about 50at%.That is, we can say that measured result also demonstrates good consistance with the result of calculation of front.That is, as seen,, the maximal value of 300nm～500nm wavelength coverage of the dR/d λ that is obtained by Ag is reduced by add the little metal of dR/d λ value of 300nm～500nm wavelength coverages such as Cu, Al, Au to Ag.Thereby, if the content of Ag is made as below the 50at%, then the maximal value of the dR/d λ in 300nm～500nm wavelength coverage can be controlled to be below 3.

For whether can obtaining enough photostability, under 40 hours conditions of the xenon lamp irradiation time of Fig. 4 (c), be that the situation of Cu and situation that the reflection horizon is Ag compare with the reflection horizon.As shown previously, the maximal value of the dR/d λ in 300nm～500nm wavelength coverage is relevant with the content substantial linear of Ag.Therefore, suppose that photostability is relevant with the content substantial linear of Ag, then quiver value 13% is the tolerance limit of wow and flutter deterioration, and this quiver value is considered to the value that can utilize reader to read.In addition, be made as the optical recording media of Ag (100at%), will carry out 40 hours postradiation background quiver values of xenon lamp and be plotted in Figure 13 for the optical recording media that the reflection horizon is made as Cu (100at%) with the reflection horizon.That is, Figure 13 is for showing the curve of following relation: under above-mentioned supposition, and Cu _(100-X)Ag _XIn the value (content of Ag: of X at%) with the relation of background quiver value.As seen from Figure 13, the upper limit that obtains the Ag content of good jitter characteristics easily is about 30at%.

Below, in embodiment 1, except that the Cu reflection horizon is become CuAg respectively _12.8And CuAg _12.9Pd _0.7In addition, in mode similarly to Example 1, produce optical recording media (below, be called " CuAg sometimes _12.8DVD-R " and " CuAg _12.9Pd _0.7DVD-R ").In addition, these optical recording medias are implemented the record of 8 times of speed after, carry out the light fastness test (wherein, xenon lamp irradiation time be made as 120 hour) identical with embodiment 1.The results are shown in the curve map of Figure 14 (a) (quiver value) and Figure 14 (b) (PI mistake).All results all can't see deterioration fully, and are all very good, and as seen, above-mentioned aldary has the effect identical with the Cu reflection horizon.

Further, to CuAg _12.8DVD-R and CuAg _12.9Pd _0.7DVD-R carries out the storage stability test.Use constant temperature and humidity cabinet (SH-641 that エスペ Star Network society makes), optical recording media was kept 875 hours in 80 ℃, relative humidity 85%, carry out storage stability test (being also referred to as " durability test " sometimes) thus.Above-mentioned CuAg _12.8DVD-R and CuAg _12.9Pd ₀₇The curve map that the results are shown in Figure 15 (a) (quiver value) and Figure 15 (b) (PI mistake) that DVD-R tests at the storage stability under hot and humid.In Figure 15 (a) and (b), CuAg _12.8DVD-R is designated as " CuAg _12.8", CuAg _12.9Pd _0.7DVD-R is designated as " CuAg _12.9Pd _0.7".Both equal deteriorations are very little, and are very good.

[embodiment 7 and embodiment 8]

Remove CuAg with embodiment 6 _12.8Reflection horizon or CuAg _12.9Pd _0.7The reflection horizon becomes CuAg _12.8Zn _1.1Reflection horizon and CuAg _12.9Zn _10.6Beyond the reflection horizon, in other all identical modes with embodiment 6, produce optical recording media (below, be sometimes referred to as CuAg _12.8Zn _1.1DVD-R (embodiment 7), CuAg _12.9Zn _10.6DVD-R (embodiment 8)).

To optical recording media separately, implement photostability experiment (the results are shown in Figure 14 (a) and Figure 14 (b)) and the storage stability under hot and humid is tested (the results are shown in Figure 15 (a) and Figure 15 (b)) in the mode identical with embodiment 6.

Has the CuAg of embodiment 6 with the reflection horizon _12.8Situation and reflection horizon have CuAg _12.9Pd _0.7Situation identical, no matter in the photostability experiment, still in the storage stability test, the reflection horizon has CuAg _12.8Zn _1.1Situation in, demonstrate very good characteristic.With respect to this, compare with other optical recording media, have CuAg in the reflection horizon _12.9Zn _10.6Situation in, can see that storage stability under hot and humid has the tendency of some deteriorations.Its reason is not very clear, but thinks that the leeway of improvement is arranged.

[embodiment 9]

Melting method in a vacuum according to following explanation carries out the making of sputtering target.

At first, in the high frequency smelting furnace, with Cu and the Ag crucible of packing into, when vacuumizing fully, fuse with predetermined ratio.At this moment, as element kind X, when adding Pd (embodiment 6), Al, Cr, Ni (embodiment 9) and In, Sn (embodiment 10 described later), add with Cu, Ag with predetermined ratio in advance.On the other hand, as element kind X, when adding Zn (

embodiment

7,8,9 and embodiment described later 10), fully fuse the back interpolation at Cu and Ag.This is because if from beginning most to load the high Zn of vapor pressure, then owing to volatilize, composition does not reach setting.

Melt temperature in the stove is made as 1100 ℃～1200 ℃.Crucible uses C, Al ₂O ₃, MgO or ZrO ₂Deng.

Liquation is cast to inner face has been coated with in the mold of Fe that aluminium oxide or magnesium are talcum or C system, cast thus.

In order to prevent the mold shrinkage cavity, before injection,, an one direction is solidified from the bottom to top by preheating with emitting oral area to be heated to about 300 ℃～about 500 ℃ in advance.

In mold, make the fused mass cooling, solidify, thereby produce ingot bar, utilize calender with this ingot bar calendering, thereby produce the tabular alloy of 90 (mm) * 90 (mm) * 8.1 (mm).

, utilize electric furnace thereafter, with the states of Ar gas being enclosed at 400 ℃～500 ℃, should tabular alloy thermal treatment about 1 hour～about 1.5 hours, further utilize pressing machine correction warpage thereafter.

In addition, to revised plate being carried out the line cutting, make it become article shape.Use the front surface of water-fast pouncing paper abrasive article, adjust surface roughness, thereby finally produce the sputtering target of Cu alloy.

In addition, vacuum tightness remains on 1.3 * 10 ^-2Pa (1 * 10 ^-4Torr) Yi Xia high vacuum.Its purpose is, because be easy to contain oxygen in the liquation of Ag, Cu, therefore under reduced pressure keeps carrying out deoxidation in the process of liquation.But,, therefore according to circumstances carry out various atmosphere adjustment because under reduced pressure Ag volatilizees.

With above-mentioned method, produce sputtering target with the composition shown in the following table 2.

Table 2

Target is formed	Time 0	Behind 80 ℃ of 80%RH 24hr	The variation of reflectivity (%)
Target is formed	Time 0	Behind 80 ℃ of 80%RH 24hr	The variation of reflectivity (%)	Cu _87.2 Ag _12.8	88.4	64.7	-26.8
Cu _84.8 Ag _12.7 Al _2.5	90.6	85.2	-5.96	Cu _87.2 Ag _12.8	88.4	64.7	-26.8
Cu _84.8 Ag _12.7 Al _2.5	90.6	85.2	-5.96	Cu _76.1 Ag _12.0 Al _11.9	88.2	82.4	-6.58
Cu _86.1 Ag _12.8 Zn _1.1	94.2	92.1	-2.23	Cu _76.1 Ag _12.0 Al _11.9	88.2	82.4	-6.58
Cu _86.1 Ag _12.8 Zn _1.1	94.2	92.1	-2.23	Cu8 _1.8 Ag _12.9 Zn _5.3	90.3	86.4	-4.32
Cu _85.9 Ag _12.8 Cr _1.3	91.0	86.4	-5.05	Cu8 _1.8 Ag _12.9 Zn _5.3	90.3	86.4	-4.32
Cu _85.9 Ag _12.8 Cr _1.3	91.0	86.4	-5.05	Cu _80.7 Ag _12.7 Cr _6.6	86.1	82.8	-3.83
Cu _86.0 Ag _12.8 Ni _1.2	85.3	82.5	-3.28	Cu _80.7 Ag _12.7 Cr _6.6	86.1	82.8	-3.83
Cu _86.0 Ag _12.8 Ni _1.2	85.3	82.5	-3.28	Cu _81.3 Ag _12.8 Ni _5.9	81.7	79.1	-3.18

For target and the storage stability of sputtered film and the tendency of reflectivity of investigating above-mentioned composition, carry out following experiment.That is, form the sputtered film of 150nm with following sputtering condition on glass substrate, this sputtered film is slightly thicker than common thickness.In addition, measure from the reflectivity of the light time of face side irradiation 650nm.When film forming is finished and temperature be 80 ℃, relative humidity be 80% hot and humid keep 24 hours down after, implement the mensuration of its reflectivity.The measurement result of the reflectivity when finishing according to film forming, reflectivity is formed relevant with target as can be known.In addition, hot and humidly keep down after 24 hours and the variation of the reflectivity of film forming when finishing, can obtain the result of the test of very strict storage stability by being determined at.In addition, the optical splitter that is used for the mensuration of above-mentioned reflectivity is the UV-3100PC that Shimadzu Seisakusho Ltd. makes.

＜sputtering condition 〉

(ULVAC) BC4341 that sputter equipment=ア Le バ Star Network is made

The vacuum tightness that reaches=5 * 10 ^-4Pa

Ar gas pressure=0.3Pa

Power input during sputter (maximal value)=200W

The measurement result of the reflectivity when film forming is finished, the hot and humid measurement result of the reflectivity after 24 hours and the measurement result of reflectance varies of keeping are down listed in table 2.In table 2, what " time 0 " was represented is " measurement result of the reflectivity when film forming is finished ".In addition, in table 2, " behind 80 ℃ of 80%RH24hr " what represent is " the hot and humid measurement result that keeps the reflectivity after 24 hours down ".In addition, in table 2, what " reflectance varies " represented is " measurement result of reflectance varies ".

In table 2, to compare with the binary system of Cu, Ag, the effect of the raising of the storage stability that the interpolation of element kind X causes clearly manifests.That is, for example, for Cu _87.2Ag _12.8, reflectivity be reduced to 26.8%, the tendency that becomes big is arranged, with respect to this, Cu _84.8Ag _12.7Al _2.5, Cu _86.1Ag ₁₂₈Zn _1.1, Cu _85.9Ag _12.8Cr _1.3, Cu _85.3Ag _12.8Ni _1.2The reduction of reflectivity be respectively 5.96%, 2.23%, 5.05%, 3.28%, reduce lessly.In addition,, in table 2, as can be known, in the situation of Al, Zn, Cr, can obtain higher reflectivity (the last 90%) as element kind X, particularly among these, preferred Al and Zn aspect high reflectance.On the other hand, as utilize the Al checking, when the alloy of CuAg adds element kind X,, the big tendency of reflectance varies then occurs if the content of element kind X surpasses 10at%.

In addition, as element kind X, so long as more than one, then several can, use in the situation of two or more metallic elements, its summation is set at that 10at% is following to get final product.

[embodiment 10]

In the mode identical, produce sputtering target with composition that following table 3 puts down in writing with embodiment 9.Further, in order to investigate the oxidative resistance and the corrosion resistance of this sputtering target and this sputtered film, carry out following experiment.That is, identical with embodiment 9, sputtered film is set on glass substrate.In addition, with similarly to Example 9 method measure be arranged on the reflectivity of the above-mentioned sputtered film on the glass substrate after, be the H of 100ppm in concentration ₂Kept 2 hours in the S gas atmosphere.Once more with the reflectivity after the method mensuration maintenance similarly to Example 9.In addition, the light of the 650nm of measuring reflectance is from substrate-side incident.What obtain in the above experiment the results are shown in table 3.

In table 3, what " when the sputtered film film forming is finished " represented is the measurement result of finishing the reflectivity when forming sputtered film on glass substrate.In addition, in table 3, " exposure back " what represent is at H ₂The measurement result that keeps the reflectivity after 2 hours in the S gas atmosphere.In addition, in table 3, what " rate of change " represented is the rate of change of the reflectivity of " when the sputtered film film forming is finished " and " exposing the back ".

Target is formed (at%)	When the sputtered film film forming is finished	After the exposure	Rate of change
Target is formed (at%)	When the sputtered film film forming is finished	After the exposure	Rate of change	Cu _95.2 Ag _3.8 Zn _1.0	92.74	91.00	-1.87％
Cu _93.0 Ag _3.9 Zn _3.1	93.29	91.84	-1.55％	Cu _95.2 Ag _3.8 Zn _1.0	92.74	91.00	-1.87％
Cu _93.0 Ag _3.9 Zn _3.1	93.29	91.84	-1.55％	Cu _90.8 Ag _4.0 Zn _5.2	91.67	90.72	-1.04％
Cu _90.8 Ag _8.1 Zn _1.1	90.52	91.84	-1.46％	Cu _90.8 Ag _4.0 Zn _5.2	91.67	90.72	-1.04％
Cu _90.8 Ag _8.1 Zn _1.1	90.52	91.84	-1.46％	Cu _88.4 Ag _8.2 Zn _3.4	93.05	90.72	-2.50％
Cu _85.7 Ag _8.5 Zn _5.8	93.19	88.90	-4.60％	Cu _88.4 Ag _8.2 Zn _3.4	93.05	90.72	-2.50％
Cu _85.7 Ag _8.5 Zn _5.8	93.19	88.90	-4.60％	Cu _95.9 Ag _3.8 In _0.3	91.65	90.02	-1.78％
Cu _95.1 Ag _3.9 In _1.0	88.96	88.35	-0.69％	Cu _95.9 Ag _3.8 In _0.3	91.65	90.02	-1.78％
Cu _95.1 Ag _3.9 In _1.0	88.96	88.35	-0.69％	Cu _94.3 Ag _4.0 In _1.7	85.46	85.02	-0.52％
Cu _91.5 Ag _8.1 In _0.4	91.29	90.12	-1.28％	Cu _94.3 Ag _4.0 In _1.7	85.46	85.02	-0.52％
Cu _91.5 Ag _8.1 In _0.4	91.29	90.12	-1.28％	Cu _90.5 Ag _8.3 In _1.1	91.94	87.54	-4.79％
Cu _89.5 Ag _8.6 In _1.9	86.15	85.37	-0.91％	Cu _90.5 Ag _8.3 In _1.1	91.94	87.54	-4.79％
Cu _89.5 Ag _8.6 In _1.9	86.15	85.37	-0.91％	Cu _95.9 Ag _3.8 Sn _0.3	91.58	90.37	-1.32％
Cu _95.2 Ag _3.8 Sn _1.0	89.75	88.81	-1.05％	Cu _95.9 Ag _3.8 Sn _0.3	91.58	90.37	-1.32％
Cu _95.2 Ag _3.8 Sn _1.0	89.75	88.81	-1.05％	Cu _94.3 Ag _4.0 Sn _1.7	86.73	78.44	-9.56％
Cu _91.6 Ag _8.1 Sn _0.3	91.87	90.38	-1.62％	Cu _94.3 Ag _4.0 Sn _1.7	86.73	78.44	-9.56％
Cu _91.6 Ag _8.1 Sn _0.3	91.87	90.38	-1.62％	Cu _90.6 Ag _8.3 Sn _1.1	89.73	88.59	-1.27％
Cu _89.6 Ag _8.6 Sn _1.8	86.52	85.97	-0.64％	Cu _90.6 Ag _8.3 Sn _1.1	89.73	88.59	-1.27％

As shown in Table 3, to contain the state of the Ag below the 10at% among the Cu, contain the following element kind X of 5at%, although be exposed to H ₂Extremely harsh oxidation and corrosion test that S gas is such, the rate of change of reflectivity also can control to the very little value of several percentage points mostly.In addition, the content below 5 at% of element kind X is less than the addition that uses at present.Thus also as can be known, even element kind X is below 5 at%, also in above-mentioned reflection horizon, gives full play of oxidative resistance and improve effect and corrosion resistance raising effect.

Industrial applicibility

The present invention can compatibly utilize in the purposes such as optical recording media that optical recording media that the red semiconductor laser such as DVD ± R are used or blue semiconductor laser are used.

Although use specific mode that the present invention is had been described in detail, only otherwise break away from the intent of the present invention and scope, can carry out various variations and distortion, this is obvious to those skilled in the art.

In addition, Japanese patent application that the application proposed based on April 28th, 2005 (the special 2005-131925 of hope) and the Japanese patent application (the special 2006-124059 of hope) that proposed on April 27th, 2006 are quoted its full content by reference.

Claims

1. optical recording media, this optical recording media has on the substrate with concentric circles or spiral helicine groove at least by organic dyestuff recording layer that constitutes and the reflection horizon of containing metal, the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s, described optical recording media is characterised in that

The track space of the gathering sill on the described substrate is below the 0.8 μ m, and groove width is below the 0.4 μ m, and the recording layer thickness in the groove is below the 70nm,

In the Wool scale of the rayed condition that ISO-105-B02 provides 5 grades (light fastness test), the dyestuff conservation rate of following definitions that forms the described organic dyestuff individual layer of described recording layer is below 70%,

In the wavelength coverage of 300nm～500nm, the aerial reflectivity R in described reflection horizon is below 3 to the differential value dR/d λ (%/nm) of wavelength X,

Described dyestuff conservation rate is defined as: in the wavelength coverage of 300nm～800nm, maximum absorption wave strong point in the coated film of the organic dyestuff individual layer that forms described recording layer, the ratio of the absorbance before and after the described light fastness test, that is { (test back absorbance)/(absorbance before the test) } * 100 (%).

2. optical recording media as claimed in claim 1 is characterized in that, at least a kind of element that is selected among Cu, Au and the Al is contained in described reflection horizon, and the ratio of the total of described element is more than the 50 atom % in described reflection horizon.

3. optical recording media as claimed in claim 1 or 2 is characterized in that, at wavelength 300nm～500nm place, the aerial reflectivity in described reflection horizon is 20%～70%.

4. as each described optical recording media of claim 1～3, it is characterized in that described recording layer contains azo-metal chelate dye that the metallic ion by the azo based compound of following general formula (1) expression and Zn constitutes at least as organic dyestuff,

(1)

In general formula (1),

R ¹Expression hydrogen atom or with CO ₂R ³The ester group of expression, at this, R ³The alkyl or the naphthenic base of expression straight or branched,

R ²The alkyl of expression straight or branched,

X ¹And X ²Among at least any one the expression NHSO ₂The Y base, at this, Y represents to have the alkyl of at least 2 substituent straight or brancheds of fluorine atom, simultaneously X ¹And X ²Among another group represent hydrogen atom,

R ⁴And R ⁵Represent the alkyl of hydrogen atom, straight or branched or the alkoxy of straight or branched independently of one another,

R ⁶, R ⁷, R ⁸And R ⁹Represent that independently of one another hydrogen atom or carbon number are 1 or 2 alkyl,

In addition, H ⁺From described NHSO ₂The Y base breaks away from, and forms NSO ₂Y ^-Negative base, thus the azo based compound of described general formula (1) expression and metallic ion form coordination bond.

5. as each described optical recording media of claim 1～4, it is characterized in that described recording layer contains the cyanine based dye of following general formula (2) expression at least as organic dyestuff,

(2)

In the general formula (2),

Ring A and ring B represent to have substituent phenyl ring or naphthalene nucleus independently of one another,

R ¹⁰And R ¹¹It is 1～5 alkyl that expression independently of one another can have substituent carbon number,

R ¹², R ¹³, R ¹⁴And R ¹⁵It is 1～5 alkyl that expression independently of one another can have substituent carbon number,

R ¹⁶Expression hydrogen atom, halogen atom, cyano group or can to have substituent carbon number be 1～5 alkyl,

Q ^-The expression counter anion.

6. optical recording media as claimed in claim 4, it is characterized in that, described recording layer contains azo-metal chelate dye at least as organic dyestuff, at least a azo based compound in the group that described azo-metal chelate dye is made up of the compound that is selected from following general formula (3), (4), (5), (6) expression and the metallic ion formation of the 3d transitional element except that Zn

(6)

In general formula (3) and (5), R ²⁰The expression hydrogen atom, can have the alkyl that substituent carbon number is 1～6 straight chain, side chain or ring-type, perhaps expression can have the ester group that substituent carbon number is 1～6 the alkyl with straight chain, side chain or ring-type,

In general formula (4) and (6), R ¹⁷It is 1～6 alkyl that expression can have substituent carbon number,

R in general formula (3) and (4) ²¹To R ²⁷And the R of general formula (5) and (6) ¹⁸And R ¹⁹Represent hydrogen atom independently of one another, can have the alkyl that substituent carbon number is 1～6 straight chain, side chain or ring-type, R ¹⁸And R ¹⁹Also bonding and form ring mutually,

In general formula (3), (4), (5), (6), X ¹And X ²Among at least any one the expression NHSO ₂The Y base, at this, Y represents to have the alkyl of at least 2 substituent straight or brancheds of fluorine atom, simultaneously X ¹And X ²Among another group represent hydrogen atom,

In addition, H ⁺From described NHSO ₂The Y base breaks away from, and forms NSO ₂Y ^-Negative base, thus the azo based compound and the metallic ion of described general formula (3), (4), (5), (6) expression form coordination bond.

7. optical recording media as claimed in claim 5, it is characterized in that, described recording layer contains azo-metal chelate dye at least as organic dyestuff, at least a azo based compound in the group that described azo-metal chelate dye is made up of the compound that is selected from following general formula (3), (4), (5), (6) expression and the metallic ion formation of the 3d transitional element except that Zn

(3)

R in general formula (3) and (4) ²¹To R ²⁷And the R in general formula (5) and (6) ¹⁸And R ¹⁹Represent hydrogen atom independently of one another, can have the alkyl that substituent carbon number is 1～6 straight chain, side chain or ring-type, R ¹⁸And R ¹⁹Also bonding and form ring mutually,

8. optical recording media, this optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is perhaps carried out record with the line speed record more than the 35.0m/s less than 0.4 μ m

Described optical recording media is characterised in that, described recording layer contains azo-metal chelate dye that the metallic ion by the azo based compound of following general formula (1) expression and Zn constitutes at least as organic dyestuff,

(1)

In general formula (1),

R ²The alkyl of expression straight or branched,

9. as each described optical recording media of claim 1～8, it is characterized in that the material of following composition (A) expression is contained in described reflection horizon at least:

Form (A)

50 atom %≤Cu≤97 atom %

3 atom %≤Ag≤50 atom %

0.05 atom %≤X≤10 atom %

At this, X represents to be selected from least a kind of element in the group of being made up of Zn, Al, Pd, In, Sn, Cr, Ni, and wherein, the total amount of Cu, Ag and X is below the 100 atom %.

10. sputtering target, described sputtering target is used for the manufacturing in the reflection horizon of following optical recording media, described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, described sputtering target is characterised in that described sputtering target is made of the material that the following B of composition represents at least:

Form (B)

50 atom %≤Cu≤97 atom %

3 atom %≤Ag≤50 atom %

0.05 atom %≤X≤10 atom %

11. sputtering target as claimed in claim 10 is characterized in that, described sputtering target uses the azo-metal chelate dye that is made of the azo based compound of following general formula (1) expression and Ni, Zn metallic ion as described organic dyestuff,

(1)

In general formula (1),

R ²The alkyl of expression straight or branched,

12. azo-metal chelate dye, described azo-metal chelate dye can be used as the organic dyestuff of following optical recording media, described optical recording media has recording layer that contains organic dyestuff at least and the reflection horizon of containing metal on the substrate with concentric circles or spiral helicine groove, the shortest mark length is less than 0.4 μ m, perhaps carry out record with the line speed record more than the 35.0m/s

Described azo-metal chelate dye is characterised in that described azo-metal chelate dye is made of the azo based compound of following general formula (1) expression and the metallic ion of Zn,

(1)

In general formula (1),

R ²The alkyl of expression straight or branched,