CN1795499A - Optical recording medium - Google Patents
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- CN1795499A CN1795499A CN200480014107.6A CN200480014107A CN1795499A CN 1795499 A CN1795499 A CN 1795499A CN 200480014107 A CN200480014107 A CN 200480014107A CN 1795499 A CN1795499 A CN 1795499A
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Abstract
The invention provides a one-sided two-layer recording/reproducing type optical recording medium capable of good recording signal characteristics even from its second recording layer. The optical recording medium comprises, layered in the order mention from a recording/reproducing light incident surface side, at least a first substrate, a first recording layer mainly containing an organic pigment, a first reflection layer, a bonding layer, an inorganic protection layer, a second recording layer mainly containing an organic pigment, a second reflection layer, and a second substrate, and permits recording/reproducing by a red laser beam, characterized in that the depth of a guide groove formed in the second substrate is either 200-600 AA or 1900-2700 AA.
Description
Technical field
The present invention relates to the optical recording media of 2 layers of record regenerating type of single face.
Background technology
Except that read-only DVD optical recording medias such as (digital video disks), the DVD that can write down (DVD+RW, DVD+R, DVD-R, DVD-RW, DVD-RAM etc.) is practical.This DVD+R, DVD+RW etc. are the optical recording medias that is positioned on the extended line of the CD-R that can write down, CD-RW (recording type optical disc (compact disk)) technology in the past, for guaranteeing and the regeneration interchangeability of the special-purpose DVD of regeneration that the thickness of recording density (track pitch, signal mark (マ one Network) length) and substrate designs to meeting DVD condition ground from the CD condition.For example, in DVD+R, adopt followingly to constitute: with CD-R similarly, pigment is spin-coated on the substrate, optical recording layer is set, the information record that will be provided with metallic reflector by laminated material at its back side is with substrate and baseplate-laminating with shape.At this moment, as optical recording layer, can use the pigment material.One of feature of CD-R is the high reflectance (65%) with the standard that satisfies CD, but in the above-described configuration, for obtaining high reflectance, optical recording layer must satisfy birefraction specific under the record regenerating optical wavelength, and this is owing to be fit to the optical absorption characteristics of pigment.Even this point DVD also is same.
Therefore, proposed in read-only DVD to increasing the DVD that recording capacity has 2 layers of recording layer.Fig. 1 is the sectional drawing that the layer structure of such DVD with 2 layers of recording layer is shown.First substrate 1 and second substrate 2 are fitted by the transparent intermediate layer 5 that ultraviolet curable resin forms by clamping.Medial surface at first substrate forms first recording layer 3, forms second recording layer 4 at the second substrate medial surface.First recording layer uses the dielectric film to form as semi-transparent film.Second recording layer is made of metal film etc. and forms as reflectance coating.On first recording layer, form concavo-convex record mark, by the reflection interference effect reading and recording signal of regeneration with laser.Owing to read signal from 2 recording layers, therefore can obtain the memory capacity about maximum 8.5GB.In addition, the thickness of the 1st, second substrate is about 0.6mm respectively, and the thickness of transparent intermediate layer is about 50 μ m.The semi-transparent film that becomes first recording layer is about 30% to form according to its reflectivity, the laser that shines for second recording layer of regenerating is after about 30% of first recording layer reflection light summation is decayed, on the reflectance coating of second recording layer, reflect, after first recording layer is decayed, penetrate once more from CD.Adjusting is as the laser of reproduced light and focus is focused on first recording layer or second recording layer, if detect reflected light, and the signal of each recording layer of then can regenerating.In addition, the optical maser wavelength of record regenerating that is used in the occasion of DVD is about 650nm.
But in the above-mentioned DVD that can write down, DVD+R, DVD-R, DVD+RW etc., the recording layer that reads from single face has only one deck, in these optical recording medias, for obtaining bigger memory capacity, is necessary to make the structure from two sides regeneration.Its reason is, because the recording layer of the optical recording media of 2 layers of record regenerating type of single face has 2 layers, for focus being focused on the inner recording layer when optical sensor (ピ Star Network ア Star プ) irradiation writes with the laser tracer signal, because first recording layer makes laser attenuation, therefore there are the necessary light absorption of record of second recording layer and the problem that the light reflection can not be had both.
In addition, in patent documentation 1, proposed following invention, the purpose of this invention is: during record, face 2 recording layers that are made of organic pigment from one of optical recording media and write, during regeneration, also face 2 recording layers from one of optical recording media and read in.But this invention only rests on the formation that real estate incident is in the past write down 2 kinds of baseplate-laminatings of formation and recording film plane incident formation, does not disclose the data of in fact regenerating at 2 enterprising line items of recording layer.According to present inventor's etc. research, even adopt above-mentioned formation, can not carry out can practical record regenerating, can not solve the problem of above-mentioned light absorption reflection about second recording layer.
In addition, patent documentation 2 discloses the multi-layered type optical recording media that recording layer contains organic pigment.But, in the making of the later groove of second recording layer, use so-called 2P method by the active energy line curing resin transfer, in the manufacturing of reality, be difficult.In addition, in patent documentation 3, as embodiment 2,2 stratotype optical recording medias have been put down in writing, but recording layer is made of alloy and be to have the structure that contains the auxiliary recording layer of matching peaceful pigment, except that different with essential structure of the present invention, the influence that brings to dielectric property about the degree of depth of the gathering sill of substrate is hint not also.
Patent documentation 1: the spy opens flat 11-66622 communique
Patent documentation 2: the spy opens flat 8-124210 communique
Patent documentation 3: the spy opens the 2001-184720 communique
Summary of the invention
The objective of the invention is to, provide address the above problem a little, from second recording layer also can obtain good tracer signal characteristic, 2 layers of record regenerating type of single face optical recording media.
For the method that solves above-mentioned problem as follows.
＜1〉a kind of optical recording media; it is from record regenerating light entrance face side; be first recording layer, first reflection horizon, adhesive linkage, inorganic protective layer of principal ingredient to major general's first substrate, with the organic pigment, be that second recording layer, second reflection horizon, second substrate of principal ingredient is with this order lamination with the organic pigment; and can pass through red laser and the optical recording media of record regenerating; it is characterized in that the degree of depth that is formed on the gathering sill on second substrate is the arbitrary value among 200～600 and 1900～2700 .
＜2〉according to above-mentioned＜1〉record optical recording media, it is characterized in that, the degree of depth of the gathering sill of second substrate is 200～600 , and the maximum absorption wavelength of the absorption spectrum of second recording layer is 580～620nm, and the absorbance under the maximum absorption wavelength (Absorption) is 1.5～2.0.
＜3〉according to above-mentioned＜2〉record optical recording media, it is characterized in that the degree of depth of the gathering sill of second substrate is 200～400 .
＜4〉according to above-mentioned＜2〉optical recording media of record, it is characterized in that the thickness of second recording layer is set at least 1.5 times of thickness of first recording layer.
＜5〉according to above-mentioned＜4〉optical recording media of record, it is characterized in that the thickness of second recording layer is set to 1.5～2.5 times of thickness of first recording layer.
＜6〉according to above-mentioned＜2〉optical recording media of record, it is characterized in that the thickness in second reflection horizon is set at least 5 times of thickness in first reflection horizon.
＜7〉according to above-mentioned＜2〉record optical recording media, it is characterized in that the coefficient of heat conductivity in second reflection horizon is set to the coefficient of heat conductivity height than first reflection horizon.
＜8〉according to above-mentioned＜2〉record optical recording media, it is characterized in that, the record mark that forms on first recording layer that is formed on first substrate is formed on the slot part by the concavo-convex generation of gathering sill, portion between the record mark that forms on second recording layer on second substrate is formed on by the groove of the concavo-convex generation of gathering sill.
＜9〉according to above-mentioned＜1〉record optical recording media, it is characterized in that the degree of depth of the gathering sill that forms is 1900～2700 on second substrate, the degree of depth of the gathering sill that forms on first substrate is 1300～1700 .
＜10〉according to above-mentioned＜9〉record optical recording media, it is characterized in that the absorbance of first recording layer under maximum absorption wavelength λ max is that the absorbance of 0.5～0.8, second recording layer is 0.8～1.4.
＜11〉according to above-mentioned＜9〉record optical recording media, it is characterized in that, no matter for any one of second recording layer that forms on first recording layer that forms on first substrate, second substrate, in by the thick part of the recording layer thickness of the concavo-convex generation of gathering sill and thin part, can record regenerating in thick part.
＜12〉according to above-mentioned＜9〉record optical recording media, it is characterized in that the refractive index of the inorganic protective layer under the record regenerating wavelength is 1.0～2.4.
＜13〉according to above-mentioned＜9〉record optical recording media, it is characterized in that the transmitance in first reflection horizon during incident of record regenerating light is 40～80%.
＜14〉according to above-mentioned＜9〉record optical recording media, it is characterized in that reflector material is a silver alloy.
＜15〉a kind of recording method of optical recording media; this optical recording media is; from record regenerating light entrance face side; to major general's first substrate; with the organic pigment is first recording layer of principal ingredient; first reflection horizon; adhesive linkage; inorganic protective layer; with the organic pigment is second recording layer of principal ingredient; second reflection horizon; second substrate is with this order lamination; and can pass through red laser and the optical recording media of record regenerating; it is characterized in that; the degree of depth of the gathering sill on being formed at second substrate is on the optical recording media of the arbitrary value among 200～600 and 1900～2700 ; pass through DVD+RW; DVD+R; DVD-R; DVD-RW; any one record regenerating mode among the DVD-RAM; from first substrate-side irradiation red laser, this first recording layer and second recording layer are write down and regenerate.
＜16〉a kind of device for optical information recording, this device is to have: the rotating driving device of rotation optical information recording medium, with comprise the laser oscillator of launching laser, the laser that convergence is launched from this laser oscillator also is radiated at lens on the optical information recording medium record surface, seizure is from the optical sensor of the catoptrical optical sensor of this optical information recording medium, pass through DVD+RW, DVD+R, DVD-R, DVD-RW, at least any one record regenerating mode among the DVD-RAM, the irradiation red laser, carry out the optical recorder of record regenerating
This optical recording media is; from record regenerating light entrance face side; to major general's first substrate; with the organic pigment is first recording layer of principal ingredient; first reflection horizon; adhesive linkage; inorganic protective layer; with the organic pigment is second recording layer of principal ingredient; second reflection horizon; second substrate is with this order lamination; and can pass through red laser and the optical recording media of record regenerating; this device is characterised in that; for the degree of depth that is formed on the gathering sill on second substrate is the optical recording media of the arbitrary value among 200～600 and 1900～2700 , no matter any one of this first recording layer and second recording layer is all from the same access information of optical recording media.
The simple declaration of accompanying drawing
[Fig. 1] Fig. 1 is the sectional drawing that the structure of the read-only DVD with 2 layers of recording layer is shown.
[Fig. 2] Fig. 2 is the figure that the configuration example of optical recording media of the present invention is shown.
[Fig. 3] Fig. 3 is the figure that the layer structure example of 2 stratotype optical recording medias of the present invention is shown.
[Fig. 4] Fig. 4 is the figure of relation that the reflectivity of the groove depth of second substrate of 2 stratotype optical recording medias of the present invention and second recording layer is shown.
[Fig. 5] Fig. 5 is the figure that is used for illustrating the groove depth of 2 stratotype optical recording medias of the present invention.
[Fig. 6] Fig. 6 is the figure that is illustrated in the layer structure on first substrate that has formed gathering sill.
[Fig. 7] Fig. 7 is the figure that is illustrated in the layer structure on second substrate that has formed gathering sill.
[Fig. 8] Fig. 8 is the figure of relation that the reflectivity of the groove depth of first substrate of 2 stratotype optical recording medias of the present invention and first recording layer is shown.
[Fig. 9] Fig. 9 is the figure of relation that the instability (ジ Star one) of the groove depth of first substrate of 2 stratotype optical recording medias of the present invention and first recording layer is shown.
[Figure 10] Figure 10 is the figure that the absorption spectrum of pigment recording layer is shown.
[Figure 11] Figure 11 is the figure of absorption spectrum that the recording layer of embodiment A-1 is shown.
[Figure 12] Figure 12 is the figure of absorption spectrum that the recording layer of embodiment A-2 is shown.
[Figure 13] Figure 13 is the figure of degree of modulation that second recording layer of embodiment A-3 is shown.
The preferred plan that carries out an invention
The present invention relates to can by red laser particularly the laser of 640～665nm carry out the 2 stratotype optical recording medias with 2 layers of recording layer of record regenerating.As shown in Figure 2, optical recording media of the present invention from record regenerating light entrance face side to the major general first substrate 1, be first recording layer 3, first reflection horizon 6, adhesive linkage (transparent intermediate layer) 5, inorganic protective layer 8 of principal ingredient with the organic pigment, be that second recording layer 4, second reflection horizon 7, second substrate 2 of principal ingredient is with this order lamination with the organic pigment.In addition; the structure that for convenience of explanation, the structure that merges first substrate 1, first recording layer 3, first reflection horizon 6 is called the 1st information substrate 21, will merge second substrate 2, second recording layer 4, second reflection horizon 7, inorganic protective layer 8 is called the 2nd information substrate 22.In addition, the arrow L among the figure represents record regenerating laser.
In addition, except that the illustrated layer, optionally, the anti-sulfuric horizon, smoothing layer, antioxygen layer in bottom, Ag reflection horizon etc. can also be set.
The shape at the interface in second recording layer and second reflection horizon, because second reflection horizon directly is formed on second basal disc, therefore by the shape decision (Fig. 3, in addition, the indication sequence number among the figure is meant and the identical structure of the same indication sequence number of above-mentioned Fig. 2) of the gathering sill of second substrate.By the diffraction that the interface in second recording layer of shape of the gathering sill of this second substrate of reflection and second reflection horizon produces,, therefore be maximum because optical path difference is that λ/2 o'clock phase differential is π.When the refractive index that reflectivity is set to λ, baseplate material in the record regenerating light wavelength is set to n, when groove depth roughly satisfies (2m-1) λ/(4n) [, m is the integer 1 or 1 or more] here, meet above-mentioned condition, be diffracted to maximum, reflection light quantity is a minimum.
The gathering sill degree of depth of single-layer type DVD in the past is about 1500～1600 .On the other hand, for the optical recording media of use with the layer structure with Fig. 3 of the substrate of DVD+R standard same thickness 0.6mm, when investigating concerning between the groove depth of second substrate and the reflectivity, obtain result shown in Figure 4 by the optical system of NA0.65, LD wavelength 655nm.Though phase dependent is in the LD wavelength, if the LD wavelength coverage of normally used 640～665nm among the DVD for example can be thought and not depend on wavelength, and demonstrate the essentially identical tendency with Fig. 4.In addition, the relation of Fig. 4 is the relation that obtains by optical diffraction phenomenon, even change constituent material or its thickness, though can be influential to amplitude, the relation of groove depth and phase place is constant.
In 2 stratotype optical recording medias, the control of reflectivity is important, therefore, is necessary the groove depth of selecting reflectivity high.
The reflectivity more than 18% or 18% that requires, in scope shown in Figure 4, groove depth 400 below 400 or the scope of 1900～2700 can realize.In addition, uprise when adjusting uveal material or thickness according to reflectivity, if 600 or below 600 , the reflectivity more than 18% or 18% that can obtain requiring.In addition, so-called groove depth shown in arrow among Fig. 5, is the length from the upper opening portion that is positioned at the channel section central part to trench bottom.Among Fig. 5, a represents the groove depth of first substrate, and b represents the groove depth of second substrate.
In the optical recording media of Fig. 3, be second recording layer of principal ingredient with the organic pigment, when signal record, for obtaining the sufficient degree of modulation more than 60% or 60%, preferably the absorbance under the pigment maximum absorption wavelength λ max is set to more than 0.8 or 0.8.
In addition, the absorbance under the pigment maximum absorption wavelength λ max surpasses at 1.4 o'clock, produces accumulation of heat during record, and instability worsens, and is therefore not preferred.
Because absorbance and thickness are proportional, therefore be set to above-mentioned scope for absorbance, can control the pigment thickness according to the kind of pigment.
Then, to the degree of depth as the gathering sill of second substrate of preferred version of the present invention be that the maximum absorption wavelength of the absorption spectrum of 200～600 , second recording layer is 580～620nm, absorbance (Absorption) under maximum absorption wavelength is that 1.5～2.0 optical recording media describes.
The invention is characterized in; for carrying out record regenerating under with optical maser wavelength (about 650nm) at DVD at least; select the recording materials of maximum absorption wavelength in the scope of 580～620nm of the absorption spectrum of second recording layer; according to the absorbance under this maximum absorption wavelength is the thickness that second recording layer is controlled on 1.5～2.0 ground; second recording layer is arranged between the layer (second reflection horizon and inorganic protective layer) that contains the inorganic material that is difficult to be out of shape; when making the shape of record mark neat; the degree of depth of the gathering sill of second substrate is set to 200～600 ; thus, make 2 layers of record regenerating of single face become possibility.When absorbance less than 1.5, can not obtain good degree of modulation, surpass at 2.0 o'clock, the problem of instability variation is then arranged.
In the present invention, for the 1st information substrate with first recording layer, make and the same formation of single recording layer medium (DVD+R etc.) in the past that will be formed at first recording layer, first reflection horizon and second baseplate-laminating on first substrate, base plate deformation when thus, multiple interference effect by first recording layer, two interfaces and mark form obtains reflectivity and tracer signal degree of modulation (contrast).
In addition; for the 2nd information substrate with second recording layer; optical absorption characteristics by the substrate groove shape and second recording layer; obtain reflectivity and tracer signal degree of modulation (contrast); simultaneously; by second recording layer being arranged between the layer (second reflection horizon and inorganic protective layer) that contains the inorganic material that is difficult to be out of shape, make the shape of record mark neat.
For obtaining such effect, preferably the thickness of second recording layer is set to 1.5～2.5 times of thickness of first recording layer.When the film thickness difference of recording layer breaks away from this scope, because the easy degree difference of diffusion of record mark with identical Write strategy (ス ト ラ テ ジ) (the led pulse pattern of recording laser), is difficult for being recorded on 2 recording layers.
In addition, the film build method of recording layer is generally the method that spin coating is dissolved in the pigment in the coating solvent, and during film forming, portion's chromogenesis film thickness is poor between slot part and groove on the substrate that has formed gathering sill.Pigment thickness among so-called the present invention, short of specifying then is meant portion's pigment thickness altogether between slot part and groove, that is, the pigment thickness of portion is average between slot part and groove.Its value can easily be converted by absorbance (Absorption) and absorptivity.
The layer structure that has formed on first substrate of gathering sill is shown in Fig. 6.In addition, refer to the identical structure of same indication sequence number with above-mentioned Fig. 2 for Fig. 6 and indication sequence number among Fig. 7.In this programme, the record mark 9 that is formed at first recording layer is preferably formed in the slot part 10 of first substrate.
On the other hand, the layer structure that has formed on second substrate of gathering sill is shown in Fig. 7.The record mark 9 that is formed at second recording layer is preferably formed between the groove of second substrate portion 11.
More preferably, be purpose with the reflection strength that improves second reflection horizon, it is formation more than 5 times or 5 times that the second reflection horizon thickness is set to respect to the first reflection horizon thickness.When the pigment thickness was blocked up, heat conduction variation, record mark were difficult to expansion.For example, as mentioned above, when the thickness of second recording layer is set to 1.5～2.5 times of thickness of first recording layer, in second recording layer, compare with first recording layer, record mark is difficult to expansion.Therefore, the thickness in second reflection horizon by abutting against second recording layer is set to thicker than the thickness in first reflection horizon, can make the 1st consistent with the mark degree of expansion of second recording layer.In addition, above-mentioned multiplying power does not have the special upper limit, but thicken to a certain degree or its when above, reflection strength becomes state of saturation, therefore, can select more than 5 times or 5 times and does not produce the suitable multiplying power of the waste in the manufacturing.
In addition, the coefficient of heat conductivity in second reflection horizon is set to the coefficient of heat conductivity height than first reflection horizon,, also can obtain same effect by using than the high material of the first reflector material coefficient of heat conductivity as second reflector material that is.
In addition, as Fig. 6, shown in Figure 7, the groove shape that is formed at the 1st and second substrate is also inequality.4.7GB, the DVD+R of 0.74 μ m spacing, the occasion of DVD-R, preferred groove depth 1000～2000 of the first substrate groove shape, groove width (bottom width) 0.2～0.3 μ m.As shown in Figure 6, because the tendency that exists pigment to fill in groove when spin-coating film, so the interface shape in pigment recording layer and reflection horizon decides by this loading and substrate groove shape, and this is that above scope is suitable because if will utilize boundary reflection.
On the other hand, the second substrate groove shape as previously mentioned, is necessary to be set to groove depth 200～600 , preferred 0.2～0.4 μ m of groove width.As shown in Figure 7, the interface shape in pigment recording layer and reflection horizon is by the decision of substrate groove shape, and this is that above scope is suitable because if will utilize boundary reflection.When 1st, any one of second substrate, groove depth were darker than above-mentioned groove shape scope, reflectivity all reduced easily, in addition, groove depth is when shallow or groove width breaks away from above-mentioned groove shape scope than above-mentioned groove shape scope, and the shape of the record mark of formation is difficult to unanimity, increases instability easily.
Preferably the pigment thickness is, first recording layer (slot part) is 400～1000 , and second recording layer (portion between groove) is 600～2500 .When this scope of pigmented film thickness rate approaches, be difficult to obtain signal degree of modulation (contrast), on the contrary, when thick, the shape of mark is difficult to unanimity, increases instability easily.
Then, for as other preferred embodiment of the present invention to be formed at the gathering sill degree of depth on second substrate be 1900～2700 , be formed at the gathering sill degree of depth on first substrate is that the optical recording media of 1300～1700 describes.
For the optical recording media of this programme, for first recording layer, the degree of depth of gathering sill is set to about 1300～1700 .Since when spin-coating film, the tendency (Fig. 3) that exists pigment (recording layer) in groove, to fill, and therefore the shape at the interface in first recording layer and first reflection horizon is decided by the shape and the pigment loading of the gathering sill of this first substrate.If degree of depth less than 1300 of the gathering sill of first recording layer, the instability during record worsens, and when bigger than 1700 , reflectivity reduces.
Fig. 8, Fig. 9 illustrate the gathering sill degree of depth of first substrate that uses medium identical with the medium of the determination data that obtains above-mentioned Fig. 4 and optics system mensuration and the figure of reflectivity and instable relation.Learn from Fig. 8, owing to reduce with the increase reflectivity of groove depth, so about preferred 1700 of the upper limit of groove depth.In addition, learn that reducing instability with groove depth increases from Fig. 9, so about preferred 1300 of the lower limit of groove depth.In addition, if the LD wavelength coverage of normally used 640～665nm among the DVD even change material, the thickness of wavelength or each layer, also demonstrates same tendency.
The absorbance of first recording layer under maximum absorption wavelength λ max preferably is set to 0.5～0.8 scope.If absorbance less than 0.5 is difficult to obtain sufficient degree of modulation, surpass at 0.8 o'clock, produce accumulation of heat during record, instability worsens.
In this programme, as the recording portion 12 that the arrow of Fig. 3 is represented, any one of first, second recording layer all preferably is formed in the thick part of pigmented film thickness that is formed at the substrate recess and writes down such formation.This is to be difficult to obtain sufficient degree of modulation because of the part at the pigmented film thin thickness that is formed at the substrate recess.
As recording method to optical recording media of the present invention, can adopt the mark lengths modulation record same with in the past DVD+R, DVD-R, but form Write strategy that mark uses, be that the led pulse of recording laser preferably changes at second recording layer and first recording layer.As mentioned above, this is because the degree of expansion of mark is different at each recording layer.Particularly, preferably forming the recording laser led pulse time that the signal mark of same length uses is set to following relation.
Ws2>Ws1
Ws2: form the recording laser led pulse time that the signal of short mark lengths is used on second recording layer.
Ws1: form the recording laser led pulse time that the signal of short mark lengths is used on first recording layer.
In addition, in DVD+R,, adopt and 1 signal post is remembered into the so-called multiple-pulse Write strategy of line item laser radiation, even the present invention also preferably uses this method with a plurality of led pulses for long letter labelled notation particularly such as 14T.When carrying out the multiple-pulse record, preferably the multiple-pulse width when second recording layer writes down is set to shorter than the multiple-pulse width when first recording layer writes down.
In addition, by the information relevant with these record conditions is recorded in gathering sill in advance, adopt the setting of the record condition that drives to become easy.That is,,, carry out printing condition setting, can avoid owing to departing from the mistake that record condition produces by reading above-mentioned record condition information with driving when medium recording.
＜constitute
Below, the material that optical recording media of the present invention is used describes particularly.
Optical recording media of the present invention and DVD+R, CD-R are same, multiple interference effect by recording layer two interfaces becomes the formation that obtains high reflectance, as recording layer, under the record regenerating wavelength, refractive index n is big, the smaller optical characteristics of absorption coefficient k is necessary.Preferred range is n〉2,0.03＜k＜0.2.The characteristic of the long wavelength end of the optical absorption band of such optical characteristics by utilizing pigmented film obtains.
Figure 10 illustrates the absorption spectrum of pigment recording layer.In Figure 10, c represents the maximum light absorption wavelength, and d represents the record regenerating wavelength.
As being used as the 1st, the examples of material of second recording layer, can enumerate, match peaceful class pigment, the phthalocyanines pigment, pyrans class sulfo-pyrans class pigment, ア ズ レ ニ ゥ system (azulenium) class pigment, ス Network ア リ リ ゥ system (suarylium) class pigment, azo class pigment, first chelate class pigment, Ni, metal-complexing salt pigments such as Cr, naphthoquinones class anthraquinone pigments, the indophenols pigment, indoaniline class pigment, the triphenylmethane pigment, triallyl methane class pigment, amine ジ イ Application モ ニ ゥ system (diimmonium) class pigment and nitroso compound.
Wherein, the dye compound of the desired optical that obtains easily with optical maser wavelength (about 650nm) at 580～620nm, at DVD as the maximum absorption wavelength of the absorption spectrum of film, from the easiness of the adjustment of the film forming that adopts solvent application, optical characteristics, preferably from four azepine porphyrazine (Tetraazaporphyrazine) pigments, match at least a kind that peaceful pigment, azopigment, ス Network ア リ リ ゥ system class pigment are selected.
In addition, so-called is principal ingredient with the organic pigment, is meant to guaranteeing that good recording uses the pigment of abundant amount, but removes adjuvants such as the bonding agent that optionally adds or stabilizing agent usually, makes the recording layer that only contains pigment.
The material of the substrate of Shi Yonging is selected arbitrarily in the various materials that can use from optical recording substrate in the past in the present invention.
As examples of material, can enumerate glass and pottery such as the such vinyl chloride resins such as acrylic resin, Polyvinylchloride or vinyl chloride copolymer of polymethylmethacrylate, epoxy resin, polycarbonate resin, amorphous polyolefin resin, vibrin, soda-lime glass.Wherein, from viewpoints such as dimensional stability, the transparency and planarityes, preferred plexiglass, polycarbonate resin, epoxy resin, amorphous polyolefin resin, vibrin and glass etc., particularly, from the easiness of moulding, optimization polycarbonate resin the most.
In the 1st, second reflector material of the present invention, can use for the high material of the reflectivity of optical maser wavelength, as its example, can enumerate metal and semimetals such as Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ca, In, Si, Ge, Te, Pb, Po, Sn, Si, SiC.Wherein, preferably, the Au that reflectivity is high, Ag, Al.They can use separately, also can make up more than 2 kinds or 2 kinds or make alloy and use.In addition, when considering reflectivity, reliability, price etc., preferred silver alloy, can be enumerated AgCu, AgNdCu, AgPdCu, AgAuCu etc. as its concrete example.The content of silver is at least 90 weight % in the silver alloy, preferred 95 weight % or more than the 95 weight %.
The bed thickness in first reflection horizon is the scope of preferred 1000～5000 of thickness in 50～1000 , second reflection horizon.The 1st when identical with second reflector material, preferably has a film thickness difference according to above-mentioned.
The record regenerating of second recording layer uses the incident light from first substrate-side.Therefore, first reflection horizon is necessary it is the semipermeability film, when considering sensitivity, the reflectivity of first recording layer and second recording layer, and the light transmission rate in first reflection horizon preferred 40～80%.If less than 40% then can not make sufficient record regenerating light arrive second recording layer, from the viewpoint of reflectivity, recording sensitivity, existing problems.In addition, surpass at 80% o'clock, in first reflection horizon, can not obtain sufficient reflectivity.
In addition, for the reflection horizon being carried out the protection of chemical physics, also protective seam can be set.Can use ultraviolet curable resin etc. as protective layer material.
Between second recording layer and transparent intermediate layer, be purpose second recording layer is carried out protection chemistry and physics, inorganic protective layer is set.
As the examples of material of using in the inorganic protective layer, can enumerate SiO, SiO
2, MgF
2, SnO
2, ZnS, ZnS-SiO
2, Al
2O
3Deng the high dead matter of photopermeability.The preferred especially ZnS-SiO that crystallinity is low, refractive index is high
2In addition, ZnSSiO
2, Al
2O
3, SiO
2Deng the refractive index under the record regenerating wavelength preferred 1.0～2.4, more preferred 1.2～2.2.If it is below 2.2 or 2.2, little and stable, therefore preferred for the change of the reflectivity of the thickness of inorganic protective layer change.Surpass at 2.4 o'clock, because the change of the thickness of inorganic protective layer, refractive index produces big change, therefore becomes unstable.In addition, when refractive index diminishes, for obtaining predetermined reflection, then must increase the thickness of inorganic protective film, if less than 1.0, then thickness is blocked up is disadvantageous on the manufacturing cost this point.
The transparent intermediate layer that the bed thickness of protective seam is set to the scope of 100 ～2000 μ m preferably has adhesive linkage concurrently, can use the ultraviolet hardening of existing esters of acrylic acid, epoxies, polyurethanes or heat curable adhesive etc.In addition, the method for fitting by slide also can.
Below, the manufacture method of optical recording media of the present invention is described.But the manufacture method of optical recording media of the present invention is not limited thereto.
Formed on the surface on first substrate of groove line and/or groove and formed first recording layer, by vacuum film-forming method the reflection horizon has been set thereon again, made the 1st information substrate by the coating film forming method.Then, formed on the surface on second substrate of groove line and/or groove and formed the reflection horizon, be provided with after second recording layer by the coating film forming method thereon again, formed inorganic protective layer, made the 2nd information substrate by vacuum film-forming method by vacuum film-forming method.Then, easily make by the transparent intermediate layer that contains bonding agent the 1st, the 2nd information substrate of fitting.
That is, above-mentioned manufacture method comprises following (1)～(6) operation.
The manufacturing of＜the 1 information substrate 〉
(1) formed on the surface that to form with the pigment by the coating film forming method on first substrate of groove line and/or groove be the operation of first recording layer of principal ingredient.
(2) operation in reflection horizon is set by vacuum film-forming method on first recording layer.
The manufacturing of＜the 2 information substrate 〉
(3) formed the operation that forms the reflection horizon on second substrate of groove line and/or groove by vacuum film-forming method on the surface.
(4) on the reflection horizon, with the pigment operation of second recording layer of principal ingredient by the setting of coating film forming method.
(5) operation of inorganic protective layer is set by vacuum film-forming method on second recording layer.
＜bonding process 〉
(6) by the fit operation of the 1st information substrate and the 2nd information substrate of adhesive linkage.
＜recording layer forms operation 〉
In the present invention, film-forming method has no particular limits, and can use spin-coating method, casting, rolling method, draw and be coated with (drawing げ on the I) method, vacuum vapour deposition, sputtering method etc., but be the recording layer of principal ingredient with the pigment by the setting of coating film forming method usually.That is, be coated on by the coating fluid that will in solvent, dissolve above-mentioned organic pigment compound and form recording layer on the substrate.As adjusting the solvent that this coating fluid is used, can use known organic solvent (for example, alcohol, cellosolve, halocarbon, ketone, ester etc.).In addition,, can wait and control thickness therefore preferred spin-coating method by concentration, viscosity, the baking temperature of solvent, the revolution of spin coater, the rotational time of regulating light absorbing zone as the method for coating.
＜reflection horizon forms operation 〉
In the present invention, by vacuum film-forming method the reflection horizon is set usually.That is, form the reflection horizon by the above-mentioned light reflective material of for example evaporation, sputter or ion plating.Preferably form from the viewpoint of homogeneity, productive temp by sputtering method.
＜inorganic protective layer forms operation 〉
In the present invention, on second recording layer, inorganic protective layer is set by vacuum film-forming method usually.That is, form inorganic protective layer by the above-mentioned inorganic protective material of for example evaporation, sputter or ion plating.From the preferred use sputtering method of the viewpoint of productivity, homogeneity, productive temp.
＜bonding process 〉
In the present invention, by adhesive linkage the 1st and the 2nd information substrate of fitting.That is, bonding agent is dripped to the surface of above-mentioned inorganic protective layer, when being covered the 1st information substrate from the top, after bonding agent evenly is coated with out, be cured by the ultraviolet ray irradiation.
The recording method of optical recording media of the present invention, remove by any recording mode among DVD+RW, DVD+R, DVD-R, DVD-RW, the DVD-RAM from first substrate-side to optical recording media irradiation red laser of the present invention, to this first recording layer and second recording layer write down and regenerate outside have no particular limits.Thus, can provide the enough red lasers of energy from the single face recording method of 2 stratotype optical recording medias of regenerative recording well.
In addition, device for optical information recording of the present invention is to have, the rotating driving device of rotation optical information recording medium, with contain the laser oscillator of launching laser, the laser that convergence is launched from this laser oscillator also is radiated at lens on the optical information recording medium record surface, seizure is from the optical sensor of the catoptrical optical sensor of this information recording carrier, pass through DVD+RW, DVD+R, DVD-R, DVD-RW, at least any one recording mode among the DVD-RAM, the irradiation red laser, the optical recorder that writes down and regenerate, optical recording media for the invention described above, no matter any one of this first recording layer and second recording layer is all from the same access information of optical recording media, in addition, have no particular limits.Thus, can provide can enough red lasers from the single face device for optical information recording of 2 stratotype used by optical recording medium of regenerative recording well.
Below, by embodiment and comparative example the present invention is described more specifically, but the present invention is not subjected to these
The qualification of embodiment.
＜embodiment A-1 〉
Be about 1500 , groove width to be about 0.25 μ m, track pitch be that the diameter of the gathering sill relief pattern of 0.74 μ m is that 120mm, thickness are on the polycarbonate substrate (first substrate) of 0.58mm having the degree of depth, the ス Network ア リ リ ゥ system dye compound of following structural formula 1 being represented by spin coating is dissolved in 2,2,3, the coating fluid of 3-tetrafluoropropanol is provided with first recording layer that thickness is about 600 .
The absorption spectrum of this first recording layer as shown in figure 11, maximum absorption wavelength is that 609nm, the absorbance under maximum absorption wavelength (Abs) are 0.9.
Then, on first recording layer, be sputter gas with Ar, with the thickness of about 200 Ag is set by sputtering method, form first reflection horizon, obtain the 1st information substrate.
On the other hand, be about 200 , groove width to be about 0.25 μ m, track pitch be that the diameter of the gathering sill relief pattern of 0.74 μ m is that 120mm, thickness are on the polycarbonate substrate (second substrate) of 0.58mm having the degree of depth, with Ar is sputter gas, with the thickness of about 1200 Ag is set by sputtering method, forms second reflection horizon.
Then, on this reflection horizon, it is 1.6 that limit adjusting thickness makes absorbance, the limit is with the ス Network ア リ リ ゥ system dye compound spin-coating film (maximum absorption wavelength is 609nm) of following structural formula 1 expression, again thereon, be sputter gas with Ar, with the thickness of about 1500 ZnS-SiO is set by sputtering method
2, form inorganic protective layer, obtain the 2nd information substrate.
Then, with ultraviolet hardening bonding agent (Japanese chemical drug system KARAYAD DVD003) applying the 1st information substrate and the 2nd information substrate, obtain the optical recording media of layer structure shown in Figure 2.
For above-mentioned optical recording media, use DVD evaluating apparatus (the system DDU1000 of パ Le ス テ Star Network society, wavelength: 657nm, NA:0.65), write down DVD (8-16) signal under the condition of on-line velocity 8.5m/s, under the linear velocity of 3.49m/s, regenerate when estimating, be met the structure (with reference to table 1) of DVD-ROM standard.
In addition, Write strategy is set to the multiple-pulse mode of (n-2) T, and the multiple-pulse width is set to 10/16.
[table 1]
| Characteristic | Dvd standard | First recording layer | Second recording layer |
| Record back reflection rate (R14H) | More than 18% or 18% | 20％ | 26％ |
| Degree of modulation (I14/I14H) | More than 60% or 60% | 84％ | 80％ |
| Instability | Below 8% or 8% | 7.0％ | 7.5％ |
＜embodiment A-2 〉
Except that the ス Network ア リ リ ゥ system dye compound that pigment is become following structural formula 2 expressions, similarly make optical recording media of the present invention with embodiment A-1, when carrying out, obtain and the same good result's (with reference to table 2) of embodiment A-1 with the same evaluation of embodiment A-1.
The absorption spectrum of the recording layer of this optical recording media as shown in figure 12, maximum absorption wavelength is 600nm.
[table 2]
| Characteristic | Dvd standard | First recording layer | Second recording layer |
| Record back reflection rate (R14H) | More than 18% or 18% | 18％ | 28％ |
| Degree of modulation (I14/I14H) | More than 60% or 60% | 80％ | 80％ |
＜embodiment A-3 〉
To make the absorbance (Abs) of second recording layer be 1.4～2.1 this point except that changing thickness, similarly make optical recording media of the present invention with embodiment A-1, when similarly estimating the degree of modulation of second recording layer with embodiment A-1, as shown in figure 13, under the absorbance more than 1.5 or 1.5, obtain the good degree of modulation more than 60% or 60%.
＜embodiment A-4 〉
Except that the groove depth of second substrate is set to 600 this point, similarly make optical recording media of the present invention with embodiment A-1, when similarly estimating the reflectivity of second recording layer, be 18% with embodiment A-1.
＜embodiment A-5 〉
Except that the groove depth of second substrate is set to 200 this point, similarly make optical recording media of the present invention with embodiment A-1, when similarly estimating the instability of second recording layer, be 8% with embodiment A-1.
＜Comparative examples A-1 〉
Remove the ス Network ア リ リ ゥ system dye compound that pigment is become 2 expressions of said structure formula, the groove depth of second substrate is set to beyond the 800 this point, similarly making optical recording media with embodiment A-1, when similarly estimating the reflectivity of second recording layer with embodiment A-1, is 15%.
According to the present invention, can provide from the single face side can record regenerating the 1st, the optical recording media of second recording layer.
According to the preferred version of the present invention of the coefficient of heat conductivity in the thickness of having adjusted recording layer or reflection horizon or reflection horizon, can provide can be with same Write strategy pattern recording first recording layer and the optical recording media of second recording layer.
＜Embodiment B-1 〉
Having track pitch by the injection molding method moulding is that diameter that 0.74 μ m, groove depth are about the gathering sill of 1600 is that 12cm, thickness are the disc wafer that the polycarbonate resin of 0.58mm is made, as first substrate.
Then, will be by spin- coating method 2,2,3, the pigment solution of first compound 0.03g that has dissolved ス Network ア リ リ ゥ system dye compound 0.07g, following structural formula 4 expressions of following structural formula 3 expressions among the 3-tetrafluoropropanol 10g is coated on first substrate, forms first recording layer.
Use spectrophotometer U-1000 (Hitachi's system), the absorbance that is determined at first recording layer under the wavelength 600nm is 0.6.
Then, in 100 ℃ stove, after carrying out annealing in 15 minutes, by sputter equipment (ユ Na Network シ ス society system), use AgNdCu alloy [Ag: Nd: Cu=99.0: 0.4: 0.6 (weight %)] target (コ ベ Le コ scientific research society system), under sputtering power 1.1kW, 0.7 second condition of sputtering time, on first recording layer, form first reflection horizon.The thickness that uses film evaluating apparatus ETA (ス テ ア ゲ society system) to measure first reflection horizon is 150 , uses above-mentioned spectrophotometer U-1000, and the light transmission rate that is determined at first reflection horizon under the wavelength 657nm is 52%.
On the other hand, having track pitch by the injection molding method moulding is that diameter that 0.74 μ m, groove depth are about the gathering sill of 2100 is that 12cm, thickness are the disc wafer that the polycarbonate resin of 0.58mm is made, as second substrate.
Then, by sputter equipment (ユ Na Network シ ス society system), use AgNdCu alloy [Ag: Nd: Cu=99.0: 0.4: 0.6 (weight %)] target (ユ ベ Le コ scientific research society system), under sputtering power 4kW, 1.6 seconds condition of sputtering time, on second substrate, form second reflection horizon.
Then, will be by spin- coating method 2,2,3, the pigment solution of first compound 0.03g that has dissolved ス Network ア リ リ ゥ system dye compound 0.10g, 4 expressions of said structure formula of 3 expressions of said structure formula among the 3-tetrafluoropropanol 10g is coated on second reflection horizon, forms second recording layer.
Use spectrophotometer U-1000 (Hitachi's system), the absorbance that is determined at first recording layer under the wavelength 600nm by reflectometry is 1.2.
Then use ZnSSiO
2[ZnS: SiO
2=80: 20 (moles %)] target (ジ ヤ パ Application エ Na ジ one society's system) is by sputter equipment PVC Star Network ス プ リ Application one (ユ Na Network シ ス society system), forms inorganic protective layer (refractive index 2.0).The thickness that uses the beam split ellipsometer to measure inorganic protective layer is 1800 .
2 substrates that use spin-coating laminating apparatus to fit to obtain according to above method also make the side with gathering sill opposed, make 2 stratotype optical recording medias.Bonding agent uses ultraviolet curing resin DVD-003 (Japanese chemical drug society system), fits from the first substrate-side irradiation ultraviolet radiation.
For optical recording media, use has the disc evaluation device DDU-1000 (パ Le ス テ Star Network society system) of the sensor of NA0.65, LD wavelength 657nm, carry out record with line speed record 9.2m/s at second recording layer, measure percentage modulation reflectivity and instability.Instable mensuration measuring space service time device TA320 (Yokogawa Motor society system).The results are shown in following table 3.
＜Embodiment B-2 〉
Except that the groove depth of second substrate is set to 2300 this point,, measure percentage modulation reflectivity and instability with the same 2 stratotype optical recording medias of making of Embodiment B-1.The results are shown in following table 3.
＜Embodiment B-3 〉
Except that the groove depth of second substrate is set to 2500 this point,, measure percentage modulation reflectivity and instability with the same 2 stratotype optical recording medias of making of Embodiment B-1.The results are shown in following table 3.
＜comparative example B-1 〉
Except that the groove depth of second substrate is set to 1800 this point,, measure percentage modulation reflectivity and instability with the same 2 stratotype optical recording medias of making of Embodiment B-1.The results are shown in following table 3.
＜comparative example B-2 〉
Except that the groove depth of second substrate is set to 2800 this point,, measure percentage modulation reflectivity and instability with the same 2 stratotype optical recording medias of making of Embodiment B-1.The results are shown in following table 3.
The result that can learn from table 3 is, in Embodiment B-1～3, obtained good characteristic, but any project in comparative example B1～2 is all than embodiment variation significantly.
[table 3]
| The groove depth of second substrate | Degree of modulation | Reflectivity | Instability | Judge | |
| () | (％) | σ/T(％) | |||
| | 2100 | 0.70 | 20 | 7.5 | ○ |
| | 2300 | 0.68 | 23 | 7.2 | ○ |
| | 2500 | 0.73 | 19 | 7.6 | ○ |
| Comparative example 1 | 1800 | 0.52 | 15 | 13 | × |
| Comparative example 2 | 2800 | 0.88 | 15 | 12 | × |
According to the present invention, can provide to have the 2 stratotype optical recording medias that to use the superperformance of red laser record regenerating.In addition, be set in the scheme of 1.0～2-4 in the refractive index of inorganic protective layer, even it is different to provide film to distribute, all little optical recording media of reflectivity that causes by second recording layer and reflection horizon.In addition, in the transmitance in first reflection horizon is set to 40～80% scheme, provide optical recording media with sufficient reflectivity.
Claims (16)
1. optical recording media; it is from record regenerating light entrance face side; be first recording layer, first reflection horizon, adhesive linkage, inorganic protective layer of principal ingredient to major general's first substrate, with the organic pigment, be that second recording layer, second reflection horizon, second substrate of principal ingredient is with this order lamination with the organic pigment; and can pass through red laser and the optical recording media of record regenerating; it is characterized in that the degree of depth that is formed on the gathering sill on second substrate is the arbitrary value among 200～600 and 1900～2700 .
2. according to the optical recording media of claim 1 record, it is characterized in that, the degree of depth of the gathering sill of second substrate is 200～600 , and the maximum absorption wavelength of the absorption spectrum of second recording layer is 580～620nm, and the absorbance under the maximum absorption wavelength (Absorption) is 1.5～2.0.
3. according to the optical recording media of claim 2 record, it is characterized in that the degree of depth of the gathering sill of second substrate is 200～400 .
4. according to the optical recording media of claim 2 record, it is characterized in that the thickness of second recording layer is set at least 1.5 times of thickness of first recording layer.
5. according to the optical recording media of claim 4 record, it is characterized in that the thickness of second recording layer is set to 1.5～2.5 times of thickness of first recording layer.
6. according to the optical recording media of claim 2 record, it is characterized in that the thickness in second reflection horizon is set at least 5 times of thickness in first reflection horizon.
7. according to the optical recording media of claim 2 record, it is characterized in that the coefficient of heat conductivity in second reflection horizon is set to the coefficient of heat conductivity height than first reflection horizon.
8. according to the optical recording media of claim 2 record, it is characterized in that, the record mark that forms on first recording layer that is formed on first substrate is formed on the slot part by the concavo-convex generation of gathering sill, portion between the record mark that forms on second recording layer on second substrate is formed on by the groove of the concavo-convex generation of gathering sill.
9. according to the optical recording media of claim 1 record, it is characterized in that the degree of depth of the gathering sill that forms is 1900～2700 on second substrate, the degree of depth of the gathering sill that forms on first substrate is 1300～1700 .
10. according to the optical recording media of claim 9 record, it is characterized in that the absorbance of first recording layer under maximum absorption wavelength λ max is that the absorbance of 0.5～0.8, second recording layer is 0.8～1.4.
11. optical recording media according to claim 9 record, it is characterized in that, no matter for any one of second recording layer that forms on first recording layer that forms on first substrate, second substrate, in by the thick part of the recording layer thickness of the concavo-convex generation of gathering sill and thin part, can record regenerating in thick part.
12. the optical recording media according to claim 9 record is characterized in that the refractive index of the inorganic protective layer under the record regenerating wavelength is 1.0～2.4.
13. the optical recording media according to claim 9 record is characterized in that the transmitance in first reflection horizon during incident of record regenerating light is 40～80%.
14. the optical recording media according to claim 9 record is characterized in that reflector material is a silver alloy.
15. the recording method of an optical recording media; this optical recording media is; from record regenerating light entrance face side; to major general's first substrate; with the organic pigment is first recording layer of principal ingredient; first reflection horizon; adhesive linkage; inorganic protective layer; with the organic pigment is second recording layer of principal ingredient; second reflection horizon; second substrate is with this order lamination; and can pass through red laser and the optical recording media of record regenerating; it is characterized in that; the degree of depth of the gathering sill on being formed at second substrate is on the optical recording media of the arbitrary value among 200～600 and 1900～2700 ; pass through DVD+RW; DVD+R; DVD-R; DVD-RW; any one record regenerating mode among the DVD-RAM; from first substrate-side irradiation red laser, this first recording layer and second recording layer are write down and regenerate.
16. device for optical information recording, this device is to have: the rotating driving device of rotation optical information recording medium, with comprise the laser oscillator of launching laser, the laser that convergence is launched from this laser oscillator also is radiated at lens on the optical information recording medium record surface, seizure is from the optical sensor of the catoptrical optical sensor of this optical information recording medium, pass through DVD+RW, DVD+R, DVD-R, DVD-RW, any one record regenerating mode at least among the DVD-RAM, the irradiation red laser, carry out the optical recorder of record regenerating
This optical recording media is from record regenerating light entrance face side; to major general's first substrate; with the organic pigment is first recording layer of principal ingredient; first reflection horizon; adhesive linkage; inorganic protective layer; with the organic pigment is second recording layer of principal ingredient; second reflection horizon; second substrate is with this order lamination; and can pass through red laser and the optical recording media of record regenerating; this device is characterised in that; for the degree of depth that is formed on the gathering sill on second substrate is the optical recording media of the arbitrary value among 200～600 and 1900～2700 , no matter any one of this first recording layer and second recording layer is all from the same access information of optical recording media.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP145458/2003 | 2003-05-22 | ||
| JP2003145458A JP2004348880A (en) | 2003-05-22 | 2003-05-22 | Optical recording medium |
| JP188985/2003 | 2003-06-30 |
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| Publication Number | Publication Date |
|---|---|
| CN1795499A true CN1795499A (en) | 2006-06-28 |
| CN100382177C CN100382177C (en) | 2008-04-16 |
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|---|---|---|---|---|
| JPH1166622A (en) * | 1997-08-25 | 1999-03-09 | Taiyo Yuden Co Ltd | Optical information medium and its recording and reproducing method |
| JP2001023237A (en) * | 1999-07-02 | 2001-01-26 | Pioneer Electronic Corp | Optical recording medium |
| CN1193363C (en) * | 2001-10-25 | 2005-03-16 | 株式会社理光 | Optical recording medium |
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2003
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| CN100382177C (en) | 2008-04-16 |
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