CN100372006C - Optical recording medium having three-dimensional data graphics and method for making same - Google Patents
Optical recording medium having three-dimensional data graphics and method for making same Download PDFInfo
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- CN100372006C CN100372006C CNB200410033938XA CN200410033938A CN100372006C CN 100372006 C CN100372006 C CN 100372006C CN B200410033938X A CNB200410033938X A CN B200410033938XA CN 200410033938 A CN200410033938 A CN 200410033938A CN 100372006 C CN100372006 C CN 100372006C
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Abstract
The present invention provides an optical recording medium with three-dimensional data graphics, and a manufacture method thereof. The optical recording medium with three-dimensional data graphics of the present invention comprises a base plate and a plurality of recording layers formed on the base plate, wherein each recording layer comprises a fluorescent material with low polymerization degree. Because the fluorescent materials with low polymerization degree have high quantum efficiency and stoke shift, when laser is used for reading the optical recording medium, the recording layers is excited to send out a fluorescent signal with sufficient intensity. Thus, the optical recording medium with three-dimensional data graphics of the present invention has admirable good recording sensitivity and reading characteristics under the condition of without adding any signal amplification structure or materials additionally.
Description
Technical field
The present invention is about a kind of optical record medium and manufacture method thereof, particularly about a kind of optical record medium and manufacture method thereof with three-dimensional data figure.
Background technology
Along with the maturation day by day of industries such as computing machine, communication, consumer electronics, for the also increase day by day of demand of recording medium, to reach a large amount of purposes that circulate of information with high storage capacity, small size and low manufacturing cost.Yet the storage volume of traditional magnetic recording medium is applied required, and optical record medium since have high capacity, processing procedure easily, read fast and be easy to advantage such as preservation, become the main flow of present storage audio and video information to replace magnetic record medium gradually.
In optical record medium, numerical data utilize usually the position thickness, refractive index and absorption coefficient difference and be written into and identification.Since can be parallel write or read information, so optical record medium is also convenient many than magnetic record medium in the use.In practical application, optical record medium often is formed the form of CD, similarly is CD-ROM (can only read) or CD-WORM (can write once to reach repeatedly and read), conveniently to use and to operate.Yet, in existing optical record medium with 2-D data figure, because diffraction of light limitation (light diffraction limit) makes its maximum storage capacity that can reach that certain restriction also be arranged.Though 3-5 position can be stored to a pits (pit) by the super-resolution mode that reads the wavelength mark, so that optical record medium has four times storage volume.Yet in order to carry out aforesaid way, various accurate and accurate electronics, optics and plant equipment are indispensable, thus, this manufacturing cost that gets this kind optical record medium is significantly increased and cause and can't carry out.
For obtaining the optical record medium with bigger storage volume, industry proposes a kind of optical record medium that utilizes the three-dimensional data storage method, and it utilizes the storage volume of the storage area of increase depth direction with further lifting optical record medium.By the three-dimensional data storage mode, the data storage density of optical record medium can be promoted to 10
12Position/cubic centimetre improves the ability of optical record medium data storing significantly.This three-dimensional data storage mode mainly utilizes the part of the optical storage media refractive index with three-dimensional data figure to change the purpose that reaches access data.Its principle then is to read laser because of the birefringence that different refractivity caused and the variation of polarity by detecting, carries out the binary coding of data.
Yet, because caused diffraction of its sandwich construction of optical record medium and energy loss make the fluorescence signal strength that this optical storage media produced weaken.In order to detect so faint signal, certainly will use signal detector with more powerful laser and higher sensitivity, so more can't meet the needs of existing market to optical record medium.Therefore, under the prerequisite that does not increase processing procedure degree of difficulty and manufacturing cost, promoting the fluorescence signal strength of optical record medium, is the technical emphasis of needing research badly of present three-dimensional data storage.
Please refer to Fig. 1, it is a kind of cross-sectional view of typical three-dimensional data optical record medium 10.This three-dimensional data optical record medium 10 has Layer 2 data layer 20, each layer data layer 20 is formed between a top electrode 30 and the bottom electrode 32, and utilize the top electrode 30 and the bottom electrode 32 of insulation course 40 separating adjacents, wherein, this data Layer 20 comprises the pits 22 of plural number, and having an active layer 24 in every pits 22, the composition of this active layer is mainly polystyrene (poly (p-phenylenevinylene), PPV) fluorescent material and dyestuff.This optical record medium 10 also comprises an optical signal amplification structure 80, this optical signal amplification structure 80 comprises a smooth conducting stratum (photoconductive layer) 60 and one electroluminescence layer (electroluminescent layer) 70, and this light conducting stratum 60 and electroluminescence layer 70 are formed between a top electrode 34 and the bottom electrode 36.The operator scheme of this optical record medium 10 is to provide a voltage to this optical signal amplification structure 80 earlier, when the active layer in this data Layer 20 is read by a laser light source, a more weak exciting light that is produced, can reach corresponding light conducting stratum 60 and produce a photocurrent, and this photocurrent can further cause this electroluminescence layer 70 to produce the fluorescence signal of the last one, reaches the purpose of amplification three-dimensional data optical record medium signal.
Yet, in the manufacture process of above-mentioned three-dimensional data optical record medium 10, need an extra top electrode 34, an electroluminescence layer 70, one smooth conducting stratum 60 and the bottom electrode 36 of forming to constitute this optical signal amplification structure 80, thus, increased the complexity of processing procedure and significantly improved the manufacturing cost of optical record medium.In addition, above-mentioned optical record medium must add a voltage to this optical record medium 10 when reading, and such design can't will cause optical record medium degree of difficulty in the use to increase corresponding to present general employed signal detector.
Compared to the above-mentioned three-dimensional data optical record medium that utilizes optical signal amplification structure, industry also proposes another kind and utilizes the three-dimensional data optical record medium of micromolecule fluorescent material as data Layer, to simplify the structure and the processing procedure of optical record medium.Please refer to Fig. 2, this three-dimensional data optical record medium 100 consists predominantly of the data layer 120 of a plastic base 110, plural number and the adhesive coating 130 of plural number, and wherein each data layer 120 has a plurality of data pits of being made up of micromolecule fluorescent material and energy amplification material (photoconductive material or electric conduction material) 140.Yet, because employed micromolecule fluorescent material similarly is Nile blue (nile blue), rhodamine (rhodamine), cyanine (cyanine) dyestuff, acridine (acridine), azophenlyene (phenoxazone)
Deng dyestuff, its quantum efficiency is on the low side, and collocation energy amplification material just can reach and can be caused the complicated of assembly by the fluorescence that signal detector detected so need further.In addition, the absorbing wavelength of above-mentioned micromolecule fluorescent material is near ruddiness laser (580-650nm), and the Shi Tuoke displacement (difference of excitation wavelength and absorbing light wavelength, stoke shift) less than 30nm, easily cause (crosstalk) phenomenon of crosstalking to take place thus, significantly reduce signal/noise (S/N).In addition, because the micromolecule fluorescent material easily produces concentration extinction effect (concentration quenching effect) under high concentration, can't directly be formed in the data pits in the solvent coating mode, need on the contrary to form, make process complexity increase and the production cost raising in the mode that is scattered in the macromolecule (for example: PVB or PMA).
For meeting demand in the market, the storage volume of utilizing the three-dimensional optical storing technology to promote optical record medium is imperative.Therefore, developing the fluorescent material that to have high-quantum efficiency and Shi Tuoke displacement to strengthen by laser light excited fluorescent signal strength, for optical record medium, is a crucial problem.
Summary of the invention
In view of this, the present invention has developed the optical record medium with three-dimensional data figure, do not need to add any signal amplification structure or add any light conduction or electric conduction material, the optical record medium that can obtain to have high storage capacity, low cost and high reliability.
The object of the present invention is to provide a kind of optical record medium with three-dimensional data figure, use a kind of low polymerization degree fluorescent material by recording layer with higher quantum efficiency and Shi Tuoke displacement, so can or add any light conduction or electric conduction material without any need for the signal amplification structure that adds, can be inspired the fluorescence signal of sufficient intensity, to reach purpose with high storage capacity.
Another object of the present invention also is to provide a kind of manufacture method with optical record medium of three-dimensional data figure, utilizes this method to obtain above-mentioned optical record medium.
For achieving the above object, the invention provides a kind of optical record medium with three-dimensional data figure, it comprises a substrate and plurality of records layer, and wherein this recording layer is formed on the first surface of described substrate, and comprise low polymerization degree fluorescent material with formula I structure
-(-Z-X-)
n-
Formula I
Wherein n is 2~10;
R
1, R
2, R
3, R
4, R
5, R
6And R
7Be respectively identical or different substituting group, it is hydrogen atom, alkyl, carbalkoxy or alkoxy, wherein this alkyl, carbalkoxy or alkoxy contain 1-20 carbon atom, it is straight chain or tool Zhi Jian, and have the hydrogen on one or more carbon in the low polymerization degree fluorescent material of formula (I) structure, optionally can be replaced by halogen atom.
The present invention also provides a kind of manufacture method with optical record medium of three-dimensional data figure, comprises following steps:
One substrate is provided;
On a first surface of this substrate, form the plurality of records layer, and this recording layer comprises and has the described low polymerization degree fluorescent material of formula I,
-(-Z-X-)
n-
Formula I
Wherein n is 2~10;
R
1, R
2, R
3, R
4, R
5, R
6And R
7Be respectively identical or different substituting group, it is hydrogen atom, alkyl, carbalkoxy or alkoxy, wherein this alkyl, carbalkoxy or alkoxy contain 1-20 carbon atom, it is straight chain or tool side chain, and the hydrogen on one or more carbon in the above-mentioned low polymerization degree fluorescent material with formula I structure optionally can be replaced by halogen atom.
Optical record medium and manufacture method thereof with three-dimensional data figure provided by the invention, because of plural recording layer that it comprised has used a kind of low polymerization degree fluorescent material, this low polymerization degree fluorescent material can be inspired the fluorescence signal of sufficient intensity, compared to prior art, optical record medium with three-dimensional data figure of the present invention, do not need to add any signal amplification structure or add any light conduction or electric conduction material, can obtain splendid record sensitivity and read characteristic, and described product has significantly been simplified the processing procedure of prior art, has obtained high storage capacity, low cost and high reliability optical record medium.
The above-mentioned optical record medium with three-dimensional data figure is separated with clearance layer between its each recording layer, and wherein this clearance layer is the adhesive coating or the polymeric layer of printing opacity.
Described optical record medium with three-dimensional data figure; also be included on the recording layer of the superiors and be coated with a protective seam; the refractive index of wherein said substrate, recording layer, clearance layer and protective seam is close or identical substantially; has the plurality of data hole on this recording layer; this data pits is scattered in this recording layer; and the low polymerization degree fluorescent material fills in this complex data hole; the Shi Tuoke displacement of this low polymerization degree fluorescent material is not less than 50nm; its molecular weight is between 500 to 4500; its quantum efficiency is not less than 0.02 Φ, preferably is not less than 0.1 Φ.
The above-mentioned optical record medium with three-dimensional data figure, wherein n is 3~6.
Optical record medium with three-dimensional data figure of the present invention, the opposition side of its substrate first surface has a second surface, and has the plurality of records layer on this second surface.
Optical record medium of the present invention is the read-only disc sheet, perhaps also can be only to write only disposable optical disk, and this optical record medium utilizes a blue light laser to read.
Manufacture method with optical record medium of three-dimensional data figure of the present invention, as mentioned above, also be included in and form the recording layer of clearance layer between each recording layer with space between adjacent, after finishing recording layer and clearance layer, also be included in to cover on the recording layer of the superiors and be formed with a protective seam, and these protection series of strata are covered in outermost recording layer, the recording layer damage that can prevent because of collision or rub and caused; Wherein the refractive index of this substrate, recording layer, clearance layer and protective seam is close or identical.
In the present invention, this recording layer has plurality of data hole (pit) and is scattered in this recording layer, and this low polymerization degree fluorescent material is inserted in this plurality of data hole.
The Shi Tuoke displacement of the low polymerization degree fluorescent material of mentioning in the said method is not less than 50nm, and its molecular weight is between 500 to 4500, and quantum efficiency is not less than 0.02 Φ, preferably is not less than 0.1 Φ; N wherein is 3~6.
Above-mentioned manufacture method, wherein the low polymerization degree fluorescent material is formed at after with a dissolution with solvents in this plural data hole again, because low polymerization degree fluorescent material molecular weight is between 500 to 4500, so ought directly utilize dissolution with solvents and film forming in data pits, micromolecule fluorescent material of the prior art can't take place because of the concentration extinction effect that high concentration caused, also can avoid problems such as thickness inequality that high molecular fluorescent material causes and thickness is wayward.
The optical record medium of mentioning in the manufacture method of the present invention is the read-only disc sheet, perhaps also can be only to write only disposable optical disk, and this optical record medium can utilize a blue light laser to read.
In the present invention, so-called low polymerization degree fluorescent material is meant the repetitive (repeating units) of this fluorescent chemicals, and number of repeat unit is within 2~10 scope.
Optical record medium with three-dimensional data figure of the present invention, its recording layer comprises the low polymerization degree fluorescent material with high-quantum efficiency, owing to have high-quantum efficiency (greater than 0.01 Φ), be suitable as very much the recording layer material of optical record medium with three-dimensional data figure, and its Shi Tuoke displacement (stoke shife) is greater than 50nm, can avoid the crosstalk phenomenon between reflected light and the exciting light, increase substantially the signal and the noise ratio (S/N ratio) of optical record medium, so do not need to use other signal amplification structure or material, can strengthen by laser light excited fluorescent signal, this product processing procedure is simple, being beneficial to a large amount of manufacturings, is to have high storage capacity therefore, the optical record medium of low cost and high reliability.
Below by embodiment and comparing embodiment and conjunction with figs., further specify method of the present invention, feature and advantage, but be not to be used for limiting the scope of the invention.
Description of drawings
Fig. 1 is the cross-sectional view of the three-dimensional data optical record medium of prior art;
Fig. 2 is the cross-sectional view of the three-dimensional data optical record medium of another kind of prior art;
Fig. 3 is the compact disk structure synoptic diagram with three-dimensional data figure of the preferred embodiment of the present invention;
Fig. 4 is the compact disk structure synoptic diagram with double-sided multi-layer structure of another preferred embodiment of the present invention.
Description of symbols:
10,100--three-dimensional data optical record medium;
20,120--data layer;
22,140--pits;
The 24--active layer;
30,34--top electrode;
32,36--bottom electrode;
The 40--insulation course;
60--light conducting stratum;
70--electroluminescence layer;
80--optical signal amplification structure;
The 110--plastic base;
The 130--adhesive coating;
200--has the discs of three-dimensional data figure;
The 210--substrate;
The ditch rail of 215--plural number data hole or tool concaveconvex shape;
The 220--recording layer;
The 230--clearance layer;
The 240--protective seam;
The discs of 300--double-sided multi-layer.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, but do not limit practical range of the present invention.
The present invention discloses a kind of optical record medium with three-dimensional data figure, its recording layer comprises the low polymerization degree fluorescent material with formula I structure, molecular weight has high-quantum efficiency (greater than 0.01 Φ) between 500 to 4500, its Shi Tuoke displacement (stoke shife) is greater than 50nm.
Optical record medium with three-dimensional data figure of the present invention for example can be a read-only disc sheet (ROM) or is one only to write only disposable optical disk (WORM), and it can utilize a blue light laser to be read.Please refer to Fig. 3, is example at this with a discs with three-dimensional data figure, and the method for making with optical record medium of three-dimensional data figure of the present invention is described.
At first, above-mentioned low polymerization degree fluorescent material is dissolved in the organic solvent, is mixed with a low polymerization degree fluorescent material solution, wherein employed organic solvent can be C
1-6Alcohols (alcohol), C
1-6Ketone (ketone), C
1-6Ethers (ether), halogen compounds or acid amides (amide).C wherein
1-6Alcohols can be methyl alcohol (methanol), ethanol (ethanol), isopropyl alcohol (isopropanol), diacetone alcohol (diacetonalchol; DAA), 2,2,3,3-tetrafluoropropanol (2,2,3,3-tetrafluoropropanol), ethapon (trichloroethanol), ethylene chlorhydrin (2-chloroethanol), octafluoro defend alcohol (octafluoropentanol) or hexafluoro butanols (hexafluorobutanol); C
1-6Ketone can be acetone (acetone), methylisobutylketone (methyl isobutyl ketone; MIBK), methyl ethyl ketone (methyl ethyl ketone; MEK) or 3-hydroxy-3-methyl-2-butanone (3-hydroxy-3-methyl-2-butanone); Halogen compounds can be chloroform (chloroform), methylene chloride (dichloromethane) or 1-chlorobutane (1-chlorobutane); Acid amides can be dimethyl formamide (dimethylformamide; DMF) or dimethyl acetamide (dimethylacetamide; DMA), methylcyclohexane (methylcyclohexane; MCH).
Then, above-mentioned low polymerization degree fluorescent material solution coat is had on the transparency carrier 210 of ditch rail 205 of complex data hole or tool concaveconvex shape in one, and dry, to form a recording layer 220.Wherein the material of this transparency carrier 210 can be polyester, polycarbonate (polycarbonate) or polyene.The mode that this recording layer 220 forms, can be method of spin coating, vacuum vapour deposition, spraying rubbing method, dip coated method, line rod rubbing method, modes such as mobile rubbing method, wire mark method or coil type rubbing method, be the best in the rotary coating mode wherein, its range of revolution is 500rpm~5000rpm.Formed recording layer thickness is 50nm~300nm, is the best with 70nm~250nm wherein.
Then, form a clearance layer 230 on this recording layer 220, wherein this clearance layer also has the ditch rail 205 of plural data hole or tool concaveconvex shape, and this clearance layer 230 can be the adhesive coating or the polymeric layer of a printing opacity.
Then, repeat the step of above-mentioned formation recording layer 220 and clearance layer 230, to form the recording layer 220 and the clearance layer 230 of plural number on this substrate, wherein adjacent recording layer 220 separates with this clearance layer 230.At last a protective seam 240 is fitted on the said structure, promptly finish the manufacture method of this discs with three-dimensional data figure 200, wherein the refractive index of this substrate 210, this recording layer 220, this clearance layer 230 and this protective seam 240 is for identical substantially.
Optical record medium with three-dimensional data figure of the present invention, form performance that not only can the single face multilayer also can be the optical record medium of double-sided multi-layer.Please refer to Fig. 4, the optical record medium with three-dimensional data figure of the present invention also can be formed with plural recording layer 220 and clearance layer 230 simultaneously in the two sides of this substrate 210, forms the discs 300 of a two-sided multilayer.
Synthesizing of low polymerization degree fluorescent material:
Below especially exemplified by accurate embodiment 1~12, in order to low polymerization degree fluorescent material of the present invention and preparation method thereof to be described, and be further listed in its structure of employed compound, title and conventional letter thereof in preparation embodiment of the present invention, can be more clear in the hope of making the present invention:
Compound W1:2,3-dihydrothieno[3,4-b]-1,4-dioxin (Chinese: 2,3-dihydro thiophene [3,4-b]-1,4-bioxin)
Compound W2:3,4-diaminothiophene-dihydrobromide (Chinese: 3,4-two amido thiophene two hydrobromic acids)
Precursor X1:5,7-Dibromo-2,3-dihydro-thieno[3,4-b] [1,4] dioxine (Chinese: 5,7-dibrominated 2,3-dihydro thiophene [3,4-b]-1,4-bioxin)
Precursor X2:5,7-Dibromo-2,3-diethyl-thieno-[3,4-b] pyrazine (Chinese: 5,7-dibrominated 2,3-diethyl thiophene [3,4-b] pyrazoline)
Compound Y1:2,7-Dibromo-9-isopropylidenefluorene (Chinese: 2,7-dibrominated-9-isopropylidene fluorenes)
Compound Y2:9,9 '-dioctyl-2,7-dibromofluorene (Chinese: 9,9 '-di-n-octyl-2,7-dibromo fluorenes)
Compound Y3:2,7-Dibromo-9-nonylidenefluorene (Chinese: 2,7-bromination-9-nonene base fluorenes)
Compound Y4:4,4,5,5,4 ', 4 ', 5 ', 5 '-Octamethyl-2,2 ' bi[[1,3,2] dioxaborolane] (Chinese: 4,4,5,5,4 ', 4 ', 5 ', 5 '-prestox-[2,2 '] two [[1,3,2] dioxy boron penta rings]
Precursor Z1:2,7-di-(4,4,5,5-tetramethyl-[1,3,2] dioxaborolanyl)-9-isoproylidene-fluorene2, two (4,4,5,5-tetramethyl-[1,3,2] dioxy boron penta cyclic group)-9-isopropylidene fluorenes of 7-)
Precursor Z2:2,7-di-(4,4,5,5-tetramethyl-[1,3,2] dioxaborolanyl)-9,9 '-di-n-octylfluorene (Chinese: 2, two (4,4,5,5-tetramethyl-[1,3,2] dioxy boron penta cyclic group)-9 of 7-, 9 '-di-n-octyl fluorenes)
Precursor Z3:2,7-di-(4,4,5,5-tetramethyl-[1,3,2] dioxaborolanyl) 9-nonylidene-fluorene (Chinese: 2, two (4,4,5,5-tetramethyl-[1,3,2] dioxy boron penta cyclic group)-9-nonene base fluorenes of 7-)
Prepare embodiment 1
Precursor X1's is synthetic
Get a reaction bulb, in bottle, insert the bromine (Br of 40ml acetic anhydride, 4g compound W1 and 3.1ml
2), under ice bath, react.Then, after reaction 30 minutes, add reactant liquor and slowly pour in the mixed liquor of 200ml water and ethyl acetate (1: 1).Through repeatedly extraction, dewater with magnesium sulphate again, filter and concentrate, obtain 6.82 golden solid, its purity is 80.7%, productive rate is 95.2%.Reaction process is as follows:
Prepare embodiment 2
Precursor X2's is synthetic
Get a reaction bulb, in bottle, insert ethanol, 2g (7.2mole) compound W2 and 2.58g (14.4mole) the n-bromo-succinimide (n-bromosuccinimide, NBS) of 40ml, under ice bath, react.Then, after reaction 15 minutes, add 1.74g (14.4mmol) anhydrous magnesium sulfate and 0.74g (6.5mmol) 3 again, and the 4-acetyl butyryl (3,4-hexanedione) in reaction bulb, reacted 1 hour.After reacting completely, utilize the extraction of ethyl acetate and water, dewater with magnesium sulphate, filter and concentrate, obtain the black solid of 1g, its purity is 71%, and productive rate is 31.1%.Reaction process is as follows:
Prepare embodiment 3
Precursor Z1's is synthetic
Get a reaction bulb, in bottle, insert compound Y1,2.97g (11.7mmol) compound Y4,2.15g (21.9mmol) potassium acetate and the 0.045g (5.47 * 10 of THF, the 2.0g (5.47mmol) of 40ml
-2Mmol) Pd (dppf) Cl
2CH
2Cl
2(Dichloro[1,1 '-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct), under nitrogen environment, be heated to 60 ℃.After reaction 120 hours, utilize toluene (toluene) and water (1: 1) extraction, dewater with magnesium sulphate again, filter and concentrate, and discolor with activated charcoal.Afterwards, utilize isopropyl alcohol (IPA) crystallization more again, obtain yellow solid, its productive rate is 41%.Reaction process is as follows:
Prepare embodiment 4
Precursor Z2's is synthetic
Get a reaction bulb, in bottle, insert the toluene of 20ml, compound Y2,2.97g (11.7mmol) compound Y4,2.15g (21.9mmol) potassium acetate and the 0.045g (5.47 * 10 of 3.0g (5.47mmol)
-2Mmol) Pd (dppf) Cl
2CH
2Cl
2, under nitrogen environment, be heated to 60 ℃.After reaction 120 hours, utilize toluene (toluene) and water (1: 1) extraction, dewater with magnesium sulphate again, filter and concentrate, and discolor with activated charcoal.Afterwards, utilize isopropyl alcohol (IPA) crystallization more again, obtain white crystals, its productive rate is 75%.Reaction process is as follows:
Prepare embodiment 5
Precursor Z3's is synthetic
Get a reaction bulb, in bottle, insert the toluene of 20ml, the methyl alcohol of 2ml, compound Y3,1.94g (7.64mmol) compound Y4,2.15g (21.9mmol) potassium acetate and the 0.045g (5.47 * 10 of 2.0g (4.46mmol)
-2Mmol) Pd (dppf) Cl
2CH
2Cl
2, under nitrogen environment, be heated to 60 ℃.After reaction 8 hours, utilize ethyl acetate (EA) and water (1: 1) extraction, dewater with magnesium sulphate again, filter and concentrate, obtain white solid, its productive rate is 70%.Reaction process is as follows:
Prepare embodiment 6
Synthesizing of low polymerization degree fluorescent material (1)
Get a reaction bulb, in bottle, insert 26ml toluene, 0.5g (0.74mmol) precursor Z2,0.233g (0.74mmol) precursor X1,0.02g (1.7 * 10
-2Mmol) Pd (PPh
3)
4And 2ml tetraethyl ammonium hydroxide (Et
4NOH) (be dissolved in the methyl alcohol), under nitrogen environment, be heated to 115 ℃.React after 3 hours, utilize toluene, methyl alcohol and water (10: 10: 1) extraction, dewater, filter and concentrate with magnesium sulphate.Afterwards, utilize methyl alcohol crystallization more again, obtain yellow orange powder, mean molecular weight is 2500.Reaction process is as follows:
Prepare embodiment 7
Synthesizing of low polymerization degree fluorescent material (2)
Get a reaction bulb, in bottle, insert precursor X1, the 0.02g (1.7 * 10 of precursor Z1,0.233g (0.74mmol) of toluene, the 0.34g (0.74mmol) of 26ml
-2Mmol) Pd (PPh
3)
4And the tetraethyl ammonium hydroxide (Et of 2ml
4NOH) (be dissolved in the methyl alcohol), under nitrogen environment, be heated to 115 ℃.After reaction 3 hours, utilize toluene, methyl alcohol and water (10: 10: 1) extraction, dewater with magnesium sulphate again, filter and concentrate.Afterwards, utilize methyl alcohol crystallization more again, obtain yellow powder.Reaction process is as follows:
Prepare embodiment 8
Synthesizing of low polymerization degree fluorescent material (3)
Get a reaction bulb, in bottle, insert 26ml toluene, 0.4g (0.74mmol) precursor Z3,0.233g (0.74mmol) precursor X1,0.02g (1.7 * 10
-2Mmol) Pd (PPh
3)
4And 2ml tetraethyl ammonium hydroxide (Et
4NOH) (be dissolved in the methyl alcohol), under nitrogen environment, be heated to 115 ℃.React after 3 hours, utilize toluene, methyl alcohol and water (10: 10: 1) extraction, dewater with magnesium sulphate again, filter and concentrate.Afterwards, utilize methyl alcohol crystallization more again, obtain black solid, mean molecular weight is 2297.Reaction process is as follows:
Prepare embodiment 9
Synthesizing of low polymerization degree fluorescent material (4)
Get a reaction bulb, in bottle, insert 26ml toluene, 0.4g (0.74mmol) precursor Z3,0.26g (0.74mmol) precursor X2,0.02g (1.7 * 10
-2Mmol) Pd (PPh
3)
4And 2ml tetraethyl ammonium hydroxide (Et
4NOH) (be dissolved in the methyl alcohol), under nitrogen environment, be heated to 115 ℃.React after 3 hours, utilize toluene, methyl alcohol and water (10: 10: 1) extraction, dewater with magnesium sulphate again, filter and concentrate.Afterwards, utilize methyl alcohol crystallization more again, obtain the black colloid, mean molecular weight is 912.Reaction process is as follows:
By low polymerization degree fluorescent material (1)~(4) that meet formula I of preparation embodiment 6~9 gained of the present invention, after measuring, its quantum efficiency and history separately takes off that displacement is all detailed lists in the table 1, and lists file names with its chemical constitution and repetitive quantity separately.In table 1, also be further listed in employed micromolecule fluorescent dye of prior art three-dimensional optical recording medium and quantum efficiency thereof and history and take off displacement, in the hope of the advantage place of low polymerization degree fluorescent material used in the present invention more clearly is described.
Table 1
According to the optical record medium with three-dimensional data figure of the present invention, the low polymerization degree fluorescent material that wherein has formula (I) structure, its quantum efficiency is greater than 0.01 Φ, preferable quantum efficiency can be to more than 0.1 Φ, compare with known micromolecule fluorescent dye, the quantum efficiency of low polymerization degree fluorescent material of the present invention is its 10 times, even more than 20 times.In addition, its Shi Tuoke displacement of low polymerization degree fluorescent material of the present invention is not less than 50nm, and the preferably can reach more than the 100nm, and the generation of (crosstalk) phenomenon of so can avoiding crosstalking significantly promotes signal/noise (S/N).In addition, low polymerization degree fluorescent material of the present invention does not need need be scattered in the macromolecular material as the micromolecule fluorescent material and just can use, this low polymerization degree fluorescent material can directly utilize dissolution with solvents and film forming, the medium and small molecular fluorescence material of prior art can not take place because of concentration extinction effect that high concentration caused.
Low polymerization degree fluorescent material of the present invention, step through suitable dilution and processing, promptly can be applicable in the recording layer of optical record medium (for example high density compact disc sheet), and can further increase its optical property through the fluorescent dye that mixes more than one.
Method for making with optical record medium of three-dimensional data figure
Embodiment 1 is to be example with low polymerization degree fluorescent material of the present invention (1), specifies the manufacture method with optical record medium of three-dimensional data figure of the present invention.
Embodiment 1
Get low polymerization degree fluorescent material (1) 1.8g and be dissolved in 2,2,3, in the 3-tetrafluoropropanol, and be mixed with the solution of 100g.Then, utilize the rotary coating machine that the solution coat of preparation is had on the transparent polycarbonate substrate of ditch rail of plural data hole or tool concaveconvex shape to form one first recording layer in one.The coating program of this recording layer is as follows:
Coating process: 30~500rpm 2~10 seconds
Throw processing procedure away: 1000~3000rpm 10~20 seconds
Oven dry processing procedure: 3000~5000rpm 10~20 seconds
Then, form a clearance layer on this first recording layer, wherein this clearance layer has the data hole of plural number or the ditch rail of tool concaveconvex shape.Then, repeat the method for this first recording layer of above-mentioned formation, on this clearance layer, form one second recording layer.At last, on this second recording layer, form a polycarbonate cover.
In sum, optical record medium with three-dimensional data figure of the present invention, because its employed low polymerization degree fluorescent material material has higher quantum efficiency and Shi Tuoke displacement (stoke shift), when using a laser light to read this optical record medium, this low polymerization degree fluorescent material can be inspired the fluorescence signal of sufficient intensity, thereby has quite high record sensitivity and high carrier-to-noise ratio (CNR) value.In addition, low polymerization degree fluorescent material of the present invention is dissolvable in water in the organic solvents such as alcohols, ketone, ester class, ethers, halogen compounds or acid amides, therefore utilize simple coating method (for example spraying cloth, roll extrusion coating, impregnation or rotary coating etc.), it can be coated on the substrate.So can significantly simplify the processing procedure of prior art, to obtain optical record medium with high storage capacity, low cost and high reliability.
More than described the preferred embodiments of the present invention, so it is not in order to limit the present invention.Those skilled in the art can not depart from the improvement and the variation of category of the present invention and spirit to embodiment disclosed herein.
Claims (28)
1. optical record medium with three-dimensional data figure comprises:
One substrate;
Be formed at the plurality of records layer on the first surface of this substrate, this recording layer comprises the low polymerization degree fluorescent material with formula I structure,
Z-X
n
Formula I
Wherein n is 2~10;
R
1, R
2, R
3, R
4, R
5, R
6And R
7It is respectively identical or different substituting group, be hydrogen atom, alkyl, carbalkoxy or alkoxy, wherein this alkyl, carbalkoxy or alkoxy contain 1-20 carbon atom, it is straight chain or tool side chain, hydrogen on one or more carbon of above-mentioned low polymerization degree fluorescent material with formula I structure can be replaced by halogen atom.
2. the optical record medium with three-dimensional data figure as claimed in claim 1 is wherein separated with clearance layer between each recording layer.
3. the optical record medium with three-dimensional data figure as claimed in claim 2, wherein this clearance layer is the adhesive coating or the polymeric layer of printing opacity.
4. the optical record medium with three-dimensional data figure as claimed in claim 2, it also is included on the recording layer of the superiors and is coated with a protective seam.
5. the optical record medium with three-dimensional data figure as claimed in claim 4, wherein the refractive index of this substrate, recording layer, clearance layer and protective seam is identical substantially.
6. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein this recording layer has the plurality of data hole, and this data pits is scattered in this recording layer, and this low polymerization degree fluorescent material is inserted in this complex data hole.
7. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein the Shi Tuoke displacement of this low polymerization degree fluorescent material is not less than 50nm.
8. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein the molecular weight of this low polymerization degree fluorescent material is between 500 to 4500.
9. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein the quantum efficiency of this low polymerization degree fluorescent material is not less than 0.02 Φ.
10. the optical record medium with three-dimensional data figure as claimed in claim 9, wherein the quantum efficiency of this low polymerization degree fluorescent material is not less than 0.1 Φ.
11. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein n is 3~6.
12. the optical record medium with three-dimensional data figure as claimed in claim 1, the opposition side that wherein is positioned at this substrate first surface has a second surface, and has the plurality of records layer on this second surface.
13. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein this optical record medium is the read-only disc sheet.
14. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein this optical record medium is for only writing only disposable optical disk.
15. the optical record medium with three-dimensional data figure as claimed in claim 1, wherein this optical record medium utilizes a blue light laser to read.
16. the manufacture method with optical record medium of three-dimensional data figure comprises:
One substrate is provided;
On the first surface of this substrate, form the plurality of records layer, and this recording layer includes the low polymerization degree fluorescent material of formula I structure,
-(-Z-X-)
n-
Formula (I)
Wherein n is 2~10;
Z is
Y be S, O or
R
1, R
2, R
3, R
4, R
5, R
6And R
7Be respectively identical or different substituting group, it is hydrogen atom, alkyl, carbalkoxy or alkoxy, wherein this alkyl, carbalkoxy or alkoxy contain 1-20 carbon atom, it is straight chain or tool side chain, hydrogen on one or more carbon of above-mentioned low polymerization degree fluorescent material with formula I structure can be replaced by halogen atom.
17. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16 is included in and forms the recording layer of clearance layer with space between adjacent between each recording layer.
18. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 17 after finishing recording layer and clearance layer, also is included in to cover on the recording layer of the superiors and is formed with a protective seam.
19. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 18, wherein the refractive index of this substrate, recording layer, clearance layer and protective seam is identical substantially.
20. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein this recording layer is dispersed with the plurality of data hole, and this low polymerization degree fluorescent material is inserted in this plurality of data hole.
21. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein this low polymerization degree fluorescent material is formed at after with dissolution with solvents in this plural data hole.
22. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein the Shi Tuoke displacement of this low polymerization degree fluorescent material is not less than 50nm.
23. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein the molecular weight of this low polymerization degree fluorescent material is between 500 to 4500.
24. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein the quantum efficiency of this low polymerization degree fluorescent material is not less than 0.02 Φ.
25. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 24, wherein the quantum efficiency of this low polymerization degree fluorescent material is not less than 0.1 Φ.
26. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein n is 3~6.
27. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein this optical record medium is the read-only disc sheet.
28. the manufacture method with optical record medium of three-dimensional data figure as claimed in claim 16, wherein this optical record medium is for only writing only disposable optical disk.
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CN1428344A (en) * | 2001-12-27 | 2003-07-09 | 拜尔公司 | Method for preparing neutral polyethyidenedioxythiophene and its correspondent compound |
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CN1297563A (en) * | 1998-03-18 | 2001-05-30 | 特莱第存储Ip有限责任公司 | Production of optical recording media having luminescent recording layers by embossing recording layer |
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