CN100372006C - Optical recording medium having three-dimensional data pattern and method for manufacturing the same - Google Patents

Abstract

The invention provides an optical recording medium with three-dimensional data pattern and a manufacturing method thereof. The invention relates to an optical recording medium with three-dimensional data patterns, which comprises a substrate and a plurality of recording layers formed on the substrate, wherein the recording layers comprise a low-polymerization-degree fluorescent material. Since the low-polymerization-degree fluorescent material has higher quantum efficiency and Stoke shift, the recording layer is excited to emit a fluorescent signal of sufficient intensity when the optical recording medium is read by a laser beam. Therefore, the optical recording medium with three-dimensional data pattern of the present invention has excellent recording sensitivity and reading characteristic without adding any signal amplification structure or material.

Description

Optical recording medium with three-dimensional data pattern and manufacturing method thereof

technical field

The present invention relates to an optical recording medium and its manufacturing method, in particular to an optical recording medium with three-dimensional data graphics and its manufacturing method.

Background technique

With the increasing maturity of computer, communication, consumer electronics and other industries, the demand for recording media with high storage capacity, small volume and low manufacturing cost is also increasing, so as to achieve the purpose of mass circulation of information. However, the storage capacity of traditional magnetic recording media is no longer enough, and optical recording media has gradually replaced magnetic recording media and has become the mainstream for storing audio-visual information due to its advantages of large capacity, easy manufacturing process, fast reading, and easy storage. .

In optical recording media, digital data is usually written and identified by utilizing the differences in the thickness, refractive index and absorption coefficient of the location. Since information can be written or read in parallel, optical recording media are much more convenient to use than magnetic recording media. In practical applications, the optical recording medium is usually formed into an optical disc, such as CD-ROM (read only) or CD-WORM (write once and read many times), for the convenience of use and operation. However, in the existing optical recording media with two-dimensional data patterns, due to the light diffraction limit, the maximum storage capacity that can be achieved is also limited to a certain extent. Although 3-5 bits can be stored in an information pit (pit) by reading the super-resolution method of the wavelength fraction, so that the optical recording medium has four times the storage capacity. However, in order to implement the above-mentioned method, various accurate and precise electronic, optical and mechanical devices are indispensable. As such, it is obvious that the manufacturing cost of this optical recording medium is greatly increased, making it impossible to implement.

In order to obtain an optical recording medium with a larger storage capacity, the industry proposes an optical recording medium using a three-dimensional data storage method, which further increases the storage capacity of the optical recording medium by increasing the storage space in the depth direction. With the three-dimensional data storage method, the data storage density of the optical recording medium can be increased to 10 ¹² bits/cubic centimeter, which greatly improves the data storage capacity of the optical recording medium. This three-dimensional data storage method mainly utilizes the local change of the refractive index of the optical storage medium with the three-dimensional data pattern to achieve the purpose of data access. The principle is to perform binary encoding of data by detecting the birefringence and polarity variation caused by different refractive indices of the read laser.

However, due to the diffraction and energy loss caused by the multi-layer structure of the optical recording medium, the intensity of the fluorescent signal generated by the optical storage medium is weakened. In order to detect such a weak signal, it is necessary to use a higher-power laser and a higher-sensitivity signal detector, which cannot meet the needs of the current market for optical recording media. Therefore, improving the fluorescence signal intensity of the optical recording medium without increasing the difficulty of the manufacturing process and the manufacturing cost is an urgent research focus in the current 3D data storage technology.

Please refer to FIG. 1 , which is a schematic cross-sectional structure diagram of a typical three-dimensional data optical recording medium 10 . The three-dimensional data optical recording medium 10 has two layers of data layers 20, each layer of data layers 20 is formed between an upper electrode 30 and a lower electrode 32, and an insulating layer 40 is used to separate adjacent upper electrodes 30 and lower electrodes 32, Wherein, the data layer 20 includes a plurality of information pits 22, and each information pit 22 has an active layer 24, and the active layer is mainly composed of polystyrene (p-phenylenevinylene), PPV fluorescent material and dyes. The optical recording medium 10 also includes an optical signal amplification structure 80, the optical signal amplification structure 80 includes a photoconductive layer (photoconductive layer) 60 and an electroluminescent layer (electroluminescent layer) 70, and the photoconductive layer 60 and the electroluminescent layer The excitation light layer 70 is formed between an upper electrode 34 and a lower electrode 36 . The operation mode of the optical recording medium 10 is to first provide a voltage to the optical signal amplification structure 80, when the active layer in the data layer 20 is read by a laser light source, a weak excitation light generated will be transmitted to the corresponding photoconductive layer 60 and generate a photocurrent, and the photocurrent can further cause the electroluminescent layer 70 to generate a strong fluorescent signal, thereby achieving the purpose of amplifying the signal of the three-dimensional data optical recording medium.

However, in the manufacturing process of the above-mentioned three-dimensional data optical recording medium 10, an upper electrode 34, an electroluminescence layer 70, a photoconductive layer 60 and a lower electrode 36 need to be additionally formed to form the optical signal amplification structure 80, such a Therefore, the complexity of the manufacturing process is increased and the manufacturing cost of the optical recording medium is greatly increased. In addition, when reading the above-mentioned optical recording medium, a voltage must be applied to the optical recording medium 10. Such a design cannot correspond to the signal detector commonly used at present, which will increase the difficulty of using the optical recording medium.

等染料，其量子效率偏低，所以需要进一步搭配能量增幅材料才能达到可被讯号侦测器所侦测到的荧光，导致组件的复杂化。此外，上述小分子荧光材料的吸收波长接近红光雷射(580-650nm)，且史脱克位移(激发光波长与吸收光波长的差值，stoke shift)小于30nm，如此一来易造成串扰(crosstalk)现象发生，大幅降低讯号/噪声(S/N)。另外，由于小分子荧光材料在高浓度下易产生浓度消光效应(concentration quenching effect)，无法直接以溶剂涂覆方式形成于数据坑中，反而需以分散于高分子(例如：PVB或PMA)中的方式形成，使得制程复杂度增加及生产成本提高。Compared with the above-mentioned 3D data optical recording medium using the optical signal amplification structure, the industry has also proposed another 3D data optical recording medium using small molecule fluorescent materials as the data layer to simplify the structure and manufacturing process of the optical recording medium. Please refer to FIG. 2, the three-dimensional data optical recording medium 100 mainly includes a plastic substrate 110, a plurality of data layers 120 and a plurality of adhesive layers 130, wherein each data layer 120 has a plurality of small molecule fluorescent materials and energy amplification materials ( The data pit 140 is composed of photoconductive material or electrical conductive material). However, due to the small molecule fluorescent materials used, such as nile blue (nile blue), rhodamine (rhodamine), cyanine (cyanine) dyes, acridine (acridine), phenoxazone (phenoxazone)

Such dyes have low quantum efficiency, so they need to be further matched with energy-amplifying materials to achieve fluorescence that can be detected by the signal detector, resulting in more complicated components. In addition, the absorption wavelength of the above-mentioned small molecule fluorescent material is close to red laser (580-650nm), and the stoke shift (the difference between the excitation light wavelength and the absorption light wavelength, stoke shift) is less than 30nm, which is easy to cause crosstalk (crosstalk) phenomenon occurs, greatly reducing the signal / noise (S / N). In addition, since small molecule fluorescent materials are prone to concentration quenching effect at high concentrations, they cannot be directly formed in the data pit by solvent coating, but need to be dispersed in polymers (such as PVB or PMA) The formation of the method increases the complexity of the manufacturing process and increases the production cost.

In order to meet the needs of the current market, it is imperative to use three-dimensional optical storage technology to increase the storage capacity of optical recording media. Therefore, it is a very important issue for optical recording media to develop fluorescent materials with high quantum efficiency and Stokes shift to enhance the intensity of fluorescent signals excited by laser light.

Contents of the invention

In view of this, the present invention has developed an optical recording medium with three-dimensional data graphics, which can obtain high storage capacity, low cost and high Reliable optical recording media.

The object of the present invention is to provide a kind of optical recording medium with three-dimensional data pattern, by using a kind of low polymerization degree fluorescent material with higher quantum efficiency and Stoke shift by recording layer, so can not need any additional signal The amplified structure or the addition of any light-conducting or electrically-conducting materials can be excited to generate fluorescent signals of sufficient intensity to achieve the purpose of high storage capacity.

Another object of the present invention is to provide a method for manufacturing an optical recording medium having a three-dimensional data pattern, by using the method to obtain the above-mentioned optical recording medium.

To achieve the above object, the present invention provides an optical recording medium with a three-dimensional data pattern, which comprises a substrate and a plurality of recording layers, wherein the recording layer is formed on the first surface of the substrate, and comprises structured low-polymerization fluorescent material,

-(-ZX-) _n -

Formula I

Where n is 2 to 10;

Z is

or

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different substituents, which are hydrogen atoms, alkyl groups, alkyl ester groups or alkoxy groups, wherein the alkyl, The alkyl ester group or alkoxy group contains 1-20 carbon atoms, which is a straight chain or a branched bond, and the hydrogen on one or more carbons in the fluorescent material with a structure of formula (I) can be optionally replaced by a halogen atom.

The present invention also provides a method for manufacturing an optical recording medium with three-dimensional data graphics, comprising the following steps:

providing a substrate;

A plurality of recording layers are formed on a first surface of the substrate, and the recording layers include a fluorescent material having a low degree of polymerization described in formula I,

-(-ZX-) _n -

Formula I

Where n is 2 to 10;

Z is

or

或是 X is

or

；以及Y is S, O or

;as well as

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different substituents, which are hydrogen atoms, alkyl groups, alkyl ester groups or alkoxy groups, wherein the alkyl, The alkyl ester group or alkoxy group contains 1-20 carbon atoms, which is a straight chain or branched chain, and the hydrogen on one or more carbons in the above-mentioned low-polymerization fluorescent material with the structure of formula I can be optionally replaced by a halogen atom.

The optical recording medium with three-dimensional data graphics and its manufacturing method provided by the present invention use a fluorescent material with a low degree of polymerization because of the plurality of recording layers it contains, and the fluorescent material with a low degree of polymerization can be excited to emit a fluorescent signal of sufficient intensity Compared with the prior art, the optical recording medium with three-dimensional data graphics of the present invention can obtain excellent recording sensitivity and readability without adding any signal amplification structure or adding any light-conducting or electrically-conducting materials. and the product greatly simplifies the manufacturing process of the prior art, and obtains an optical recording medium with high storage capacity, low cost and high reliability.

In the above-mentioned optical recording medium with three-dimensional data graphics, each recording layer is separated by a gap layer, wherein the gap layer is a light-transmitting adhesive layer or a polymer layer.

The optical recording medium with three-dimensional data graphics also includes a protective layer covering the uppermost recording layer, wherein the refractive indices of the substrate, recording layer, gap layer and protective layer are substantially similar or the same, and the recording layer There are a plurality of data pits on the surface, the data pits are dispersed in the recording layer, and the low-polymerization fluorescent material is filled in the multiple data pits, the Stokes shift of the low-polymerization fluorescent material is not less than 50nm, and its molecular weight is between Between 500 and 4500, its quantum efficiency is not less than 0.02Φ, preferably not less than 0.1Φ.

The above optical recording medium with three-dimensional data graphics, wherein n is 3-6.

The optical recording medium with three-dimensional data pattern of the present invention has a second surface opposite to the first surface of the substrate, and there are multiple recording layers on the second surface.

The optical recording medium of the present invention is a read-only optical disc, or may also be a write-once optical disc, and the optical recording medium is read by a blue-ray laser.

The manufacturing method of the optical recording medium with three-dimensional data graphics of the present invention, as mentioned above, also includes forming a gap layer between each recording layer to separate adjacent recording layers, after completing the recording layer and the gap layer, also includes Covering and forming a protective layer on the uppermost recording layer, and the protective layer is covering the outermost recording layer, which can prevent the recording layer from being damaged due to collision or friction; wherein the substrate, recording layer, gap layer and The refractive index of the protective layer is similar or the same.

In the present invention, the recording layer has a plurality of data pits dispersed in the recording layer, and the low polymerization degree fluorescent material is filled in the plurality of data pits.

The Stokes shift of the fluorescent material with a low degree of polymerization mentioned in the above method is not less than 50nm, its molecular weight is between 500 and 4500, and its quantum efficiency is not less than 0.02Φ, preferably not less than 0.1Φ; wherein n is 3 to 6 .

In the above-mentioned manufacturing method, wherein the fluorescent material with a low degree of polymerization is dissolved in a solvent and then formed in the plurality of data pits, since the molecular weight of the fluorescent material with a low degree of polymerization is between 500 and 4500, when directly using a solvent to dissolve and form a film In the data pit, the concentration extinction effect caused by the high concentration of the small molecule fluorescent material in the prior art does not occur, and the problems of uneven film thickness and difficult control of the thickness caused by the polymer fluorescent material can also be avoided.

The optical recording medium mentioned in the manufacturing method of the present invention is a read-only optical disc, or may also be a write-once optical disc, and the optical recording medium can be read by a blue-ray laser.

In the present invention, the so-called fluorescent material with a low degree of polymerization refers to the repeating units of the fluorescent compound, and the number of repeating units is within the range of 2-10.

The optical recording medium with three-dimensional data pattern of the present invention, its recording layer comprises the low degree of polymerization fluorescent material with high quantum efficiency, because has high quantum efficiency (greater than 0.01Φ), is very suitable as the optical recording medium with three-dimensional data pattern The recording layer material of the media, and its stoke shift (stoke shife) is greater than 50nm, which can avoid the crosstalk phenomenon between the reflected light and the excitation light, and greatly improve the signal-to-noise ratio (S/N ratio) of the optical recording medium. Therefore, there is no need to use other signal amplification structures or materials to enhance the fluorescent signal excited by laser light. The product has a simple process and is conducive to mass production. Therefore, it is an optical recording medium with high storage capacity, low cost and high reliability.

The methods, features and advantages of the present invention are further described below with reference to the examples and comparative examples together with the accompanying drawings, which are not intended to limit the scope of the present invention.

Description of drawings

Fig. 1 is the sectional structure schematic diagram of the three-dimensional data optical recording medium of prior art;

Fig. 2 is another kind of prior art three-dimensional data optical recording medium sectional structure schematic diagram;

FIG. 3 is a schematic structural view of an optical disc with three-dimensional data graphics in a preferred embodiment of the present invention;

Fig. 4 is a schematic structural diagram of an optical disc with a double-sided multi-layer structure according to another preferred embodiment of the present invention.

Mark Description:

10, 100--three-dimensional data optical recording medium;

20, 120--data layer;

22, 140--information pit;

24 - active layer;

30, 34--upper electrode;

32, 36--lower electrode;

40--Insulation layer;

60--light transmission layer;

70--electroluminescent layer;

80--optical signal amplification structure;

110--plastic substrate;

130--adhesive layer;

200--CD with three-dimensional data graphics;

210--substrate;

215--Plural data pits or grooves with concave and convex shapes;

220--record layer;

230--gap layer;

240--protection layer;

300--Double-sided multi-layer discs.

Detailed ways

The present invention will be described in detail below in conjunction with specific examples, but the implementation scope of the present invention is not limited.

The invention discloses an optical recording medium with a three-dimensional data pattern, the recording layer of which contains a low-polymerization fluorescent material having a structure of formula I, the molecular weight is between 500 and 4500, and has high quantum efficiency (greater than 0.01Φ). Stoke shift (stoke shife) greater than 50nm.

The optical recording medium with three-dimensional data patterns of the present invention can be, for example, a read-only optical disc (ROM) or a write-once optical disc (WORM), which can be read by a blue-ray laser. Please refer to FIG. 3 , where an optical disc with three-dimensional data patterns is taken as an example to illustrate the method for making an optical recording medium with three-dimensional data patterns of the present invention.

First, the above-mentioned fluorescent material with a low degree of polymerization is dissolved in an organic solvent to prepare a solution of a fluorescent material with a low degree of polymerization, wherein the organic solvent used can be a C _1-6 alcohol or a C _1-6 ketone Class (ketone), C _1-6 ether (ether), halogen compound, or amide (amide). Wherein the alcohols of C _1-6 can be methanol (methanol), ethanol (ethanol), isopropanol (isopropanol), diacetone alcohol (diacetonalchol; DAA), 2,2,3,3-tetrafluoropropanol (2 , 2,3,3-tetrafluoropropanol), trichloroethanol (trichloroethanol), 2-chloroethanol (2-chloroethanol), octafluoropentanol (octafluoropentanol), or hexafluorobutanol (hexafluorobutanol); C _1-6 ketone The class can be acetone (acetone), methyl isobutyl ketone (methyl isobutyl ketone; MIBK), methyl ethyl ketone (methyl ethyl ketone; MEK), or 3-hydroxy-3-methyl-2-butanone (3 -hydroxy-3-methyl-2-butanone); the halogen compound can be chloroform (chloroform), dichloromethane (dichloromethane), or 1-chlorobutane (1-chlorobutane); the amide can be dimethylformamide (dimethylformamide ; DMF), or dimethylacetamide (dimethylacetamide; DMA), methylcyclohexane (methylcyclohexane; MCH).

Next, the above-mentioned fluorescent material solution with a low degree of polymerization is coated on a transparent substrate 210 having a plurality of data pits or concave-convex grooves 205 , and dried to form a recording layer 220 . The material of the transparent substrate 210 can be polyester, polycarbonate or polyene. The recording layer 220 can be formed by spin coating, vacuum evaporation, spray coating, dip coating, wire bar coating, flow coating, screen printing or tape coating. Cloth method and other methods, among which the spin coating method is the best, and its rotation speed ranges from 500rpm to 5000rpm. The film thickness of the formed recording layer is 50nm-300nm, among which 70nm-250nm is the best.

Next, a gap layer 230 is formed on the recording layer 220, wherein the gap layer also has a plurality of data pits or groove tracks 205 with concave-convex shapes, and the gap layer 230 can be a light-transmitting adhesive layer or a polymer layer.

Next, repeat the above steps of forming the recording layer 220 and the gap layer 230 to form a plurality of recording layers 220 and the gap layer 230 on the substrate, wherein adjacent recording layers 220 are separated by the gap layer 230 . Finally, a protective layer 240 is pasted on the above-mentioned structure to complete the manufacturing method of the optical disc 200 with three-dimensional data patterns, wherein the refractive index of the substrate 210, the recording layer 220, the gap layer 230 and the protective layer 240 are substantially the same.

The optical recording medium with three-dimensional data graphics of the present invention can not only be expressed in the form of single-sided multilayer, but also double-sided multilayer optical recording medium. Please refer to FIG. 4 , the optical recording medium with three-dimensional data patterns of the present invention can also be formed with a plurality of recording layers 220 and gap layers 230 on both sides of the substrate 210 to form a double-sided multilayer optical disc 300 .

Synthesis of fluorescent materials with a low degree of polymerization:

Quasi-Examples 1 to 12 are given below to illustrate the fluorescent material with a low degree of polymerization of the present invention and its preparation method, and further list the structures, names and methods of the compounds used in the preparatory examples of the present invention. Representative symbols, in order to make the present invention clearer:

Compound W1: 2,3-dihydrothieno[3,4-b]-1,4-dioxin (Chinese name: 2,3-dihydrothiophene[3,4-b]-1,4-dioxin)

Compound W2: 3,4-diaminothiophene-dihydrobromide (Chinese name: 3,4-diaminothiophene dihydrobromide)

Precursor X1: 5,7-Dibromo-2,3-dihydro-thieno[3,4-b][1,4]dioxine (Chinese name: 5,7-dibromo-2,3-dihydro-thiophene[3 ,4-b]-1,4-dioxin)

Precursor X2: 5,7-Dibromo-2,3-diethyl-thieno-[3,4-b]pyrazine (Chinese name: 5,7-dibromo-2,3-diethylthiophene[3,4- b] pyrazoline)

Compound Y1: 2,7-Dibromo-9-isopropylidenefluorene (Chinese name: 2,7-dibromo-9-isopropylidenefluorene)

Compound Y2: 9,9'-dioctyl-2,7-dibromofluorene (Chinese name: 9,9'-dioctyl-2,7-dibromofluorene)

Compound Y3: 2,7-Dibromo-9-nonylidenefluorene (Chinese name: 2,7-bromo-9-nonenylfluorene)

Compound Y4: 4,4,5,5,4',4',5',5'-Octamethyl-2,2'bi[[1,3,2]dioxaborolane] (Chinese name: 4,4,5, 5,4′,4′,5′,5′-octamethyl-[2,2′]bis[[1,3,2]dioxaborolane]

Precursor Z1: 2,7-di-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl)-9-isoproylidene-fluorene2,7-bis(4,4,5,5-four Methyl-[1,3,2]dioxaborolanyl)-9-isopropylidene fluorene)

Precursor Z2: 2,7-di-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl)-9,9'-di-n-octylfluorene (Chinese name: 2,7-double (4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl)-9,9'-di-n-octylfluorene)

Precursor Z3: 2,7-di-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl) 9-nonylidene-fluorene (Chinese name: 2,7-double (4,4,5 , 5-tetramethyl-[1,3,2]dioxaborolanyl)-9-nonenylfluorene)

Prepare Example 1

Synthesis of Precursor X1

Take a reaction bottle, put 40ml of acetic anhydride, 4g of compound W1 and 3.1ml of bromine (Br ₂ ) into the bottle, and react under ice bath. Then, after reacting for 30 minutes, the reaction solution was slowly poured into a mixture of 200 ml of water and ethyl acetate (1:1). After multiple extractions, dehydration with magnesium sulfate, filtration and concentration, 6.82 gold solid was obtained with a purity of 80.7% and a yield of 95.2%. The reaction flow is as follows:

Prepare Example 2

Synthesis of Precursor X2

Take a reaction bottle, put 40ml of ethanol, 2g (7.2 mole) of compound W2 and 2.58g (14.4 mole) of n-bromosuccinimide (NBS) into the bottle, and react in an ice bath. Then, after reacting for 15 minutes, 1.74g (14.4mmol) of anhydrous magnesium sulfate and 0.74g (6.5mmol) of 3,4-hexanedione (3,4-hexanedione) were added into the reaction flask and reacted for 1 hour. After the reaction was complete, the mixture was extracted with ethyl acetate and water, dehydrated with magnesium sulfate, filtered and concentrated to obtain 1 g of a black solid with a purity of 71% and a yield of 31.1%. The reaction flow is as follows:

Prepare Example 3

Synthesis of Precursor Z1

Take a reaction bottle, put 40ml of THF, 2.0g (5.47mmol) of compound Y1, 2.97g (11.7mmol) of compound Y4, 2.15g (21.9mmol) of potassium acetate and 0.045g (5.47×10 ^-2 mmol) into the bottle ) of Pd(dppf)Cl ₂ CH ₂ Cl ₂ (Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloromethane adduct), heated to 60°C under nitrogen atmosphere. After reacting for 120 hours, extract with toluene and water (1:1), remove water with magnesium sulfate, filter and concentrate, and decolorize with activated carbon. Afterwards, recrystallization using isopropanol (IPA) gave a yellow solid with a yield of 41%. The reaction flow is as follows:

Prepare Example 4

Synthesis of Precursor Z2

Take a reaction bottle, put 20ml of toluene, 3.0g (5.47mmol) of compound Y2, 2.97g (11.7mmol) of compound Y4, 2.15g (21.9mmol) of potassium acetate and 0.045g (5.47×10 ^-2 mmol) in the bottle ) of Pd(dppf)Cl ₂ CH ₂ Cl ₂ , heated to 60°C under nitrogen atmosphere. After reacting for 120 hours, extract with toluene and water (1:1), remove water with magnesium sulfate, filter and concentrate, and decolorize with activated carbon. Afterwards, recrystallization was performed using isopropanol (IPA) to obtain white crystals with a yield of 75%. The reaction flow is as follows:

Prepare Example 5

Synthesis of Precursor Z3

Get a reaction flask, put 20ml of toluene, 2ml of methanol, 2.0g (4.46mmol) of compound Y3, 1.94g (7.64mmol) of compound Y4, 2.15g (21.9mmol) of potassium acetate and 0.045g (5.47× 10 ⁻² mmol) of Pd(dppf)Cl ₂ CH ₂ Cl ₂ , heated to 60° C. under nitrogen atmosphere. After reacting for 8 hours, the mixture was extracted with ethyl acetate (EA) and water (1:1), dehydrated with magnesium sulfate, filtered and concentrated to obtain a white solid with a yield of 70%. The reaction flow is as follows:

Prepare Example 6

Synthesis of Fluorescent Materials with Low Polymerization Degree (1)

Take a reaction bottle, put 26ml of toluene, 0.5g (0.74mmol) of precursor Z2, 0.233g (0.74mmol) of precursor X1, 0.02g (1.7×10 ^-2 mmol) of Pd(PPh ₃ ) ₄ and 2ml into the bottle Tetraethylammonium hydroxide ( _Et4NOH ) (dissolved in methanol), heated to 115°C under nitrogen atmosphere. After reacting for 3 hours, extract with toluene, methanol and water (10:10:1), remove water with magnesium sulfate, filter and concentrate. Afterwards, methanol was used for recrystallization to obtain a yellow-orange powder with an average molecular weight of 2500. The reaction flow is as follows:

Prepare Example 7

Synthesis of Fluorescent Materials with Low Polymerization Degree (2)

Take a reaction bottle, put 26ml of toluene, 0.34g (0.74mmol) of precursor Z1, 0.233g (0.74mmol) of precursor X1, 0.02g (1.7×10 ^-2 mmol) of Pd(PPh ₃ ) ₄ and 2 ml of tetraethylammonium hydroxide (Et ₄ NOH) (dissolved in methanol), heated to 115° C. under nitrogen atmosphere. After reacting for 3 hours, extract with toluene, methanol and water (10:10:1), remove water with magnesium sulfate, filter and concentrate. Afterwards, methanol was used to recrystallize to obtain a yellow powder. The reaction flow is as follows:

Prepare Example 8

Synthesis of Fluorescent Materials with Low Polymerization Degree (3)

Take a reaction bottle, put 26ml of toluene, 0.4g (0.74mmol) of precursor Z3, 0.233g (0.74mmol) of precursor X1, 0.02g (1.7×10 ^-2 mmol) of Pd(PPh ₃ ) ₄ and 2ml into the bottle Tetraethylammonium hydroxide ( _Et4NOH ) (dissolved in methanol), heated to 115°C under nitrogen atmosphere. After reacting for 3 hours, extract with toluene, methanol and water (10:10:1), remove water with magnesium sulfate, filter and concentrate. Thereafter, methanol was used for recrystallization to obtain a black solid with an average molecular weight of 2297. The reaction flow is as follows:

Prepare Example 9

Synthesis of Fluorescent Materials with Low Polymerization Degree (4)

Take a reaction bottle, put 26ml of toluene, 0.4g (0.74mmol) of precursor Z3, 0.26g (0.74mmol) of precursor X2, 0.02g (1.7×10 ^-2 mmol) of Pd(PPh ₃ ) ₄ and 2ml into the bottle Tetraethylammonium hydroxide ( _Et4NOH ) (dissolved in methanol), heated to 115°C under nitrogen atmosphere. After reacting for 3 hours, extract with toluene, methanol and water (10:10:1), remove water with magnesium sulfate, filter and concentrate. Afterwards, methanol was used to recrystallize to obtain a black colloid with an average molecular weight of 912. The reaction flow is as follows:

The low-polymerization-degree fluorescent materials (1)-(4) conforming to formula I obtained in the preparation examples 6-9 of the present invention, after measurement, their respective quantum efficiencies and Stet shifts are listed in Table 1. , and at the same time list their respective chemical structures and the number of repeating units. Table 1 also further lists the small molecule fluorescent dyes used in the prior art 3D optical recording media and their quantum efficiency and history shift, in order to more clearly illustrate the advantages of the low polymerization degree fluorescent materials used in the present invention.

Table 1

According to the optical recording medium with three-dimensional data graphics of the present invention, wherein the fluorescent material with a low degree of polymerization of the structure of formula (I) has a quantum efficiency greater than 0.01Φ, and a better quantum efficiency can reach more than 0.1Φ, which is different from known Compared with the small molecule fluorescent dyes, the quantum efficiency of the low polymerization degree fluorescent material of the present invention is 10 times, even more than 20 times. In addition, the low-polymerization fluorescent material of the present invention has a Stokes shift of not less than 50nm, preferably more than 100nm, which can avoid the occurrence of crosstalk and greatly improve the signal/noise (S/N) . In addition, the fluorescent material with a low degree of polymerization of the present invention does not need to be dispersed in a polymer material to be used like a fluorescent material with a low degree of polymerization. The concentration extinction effect of molecular fluorescent materials caused by high concentration.

The fluorescent material with a low degree of polymerization of the present invention can be applied to the recording layer of an optical recording medium (such as a high-density optical disk) through appropriate dilution and treatment steps, and can be mixed with more than one fluorescent dye to further increase its optical properties.

Optical recording medium with three-dimensional data graphics

Embodiment 1 takes the low-polymerization-degree fluorescent material (1) of the present invention as an example to specifically illustrate the manufacturing method of the optical recording medium with three-dimensional data graphics of the present invention.

Example 1

Dissolve 1.8 g of the fluorescent material (1) with a low degree of polymerization in 2,2,3,3-tetrafluoropropanol, and prepare a 100 g solution. Then, the prepared solution is coated on a transparent polycarbonate substrate having a plurality of data pits or concave-convex grooves by using a spin coater to form a first recording layer. The coating procedure of this recording layer is as follows:

Coating process: 30～500rpm 2～10 seconds

Get rid of the process: 1000～3000rpm for 10～20 seconds

Drying process: 3000～5000rpm 10～20 seconds

Then, a gap layer is formed on the first recording layer, wherein the gap layer has a plurality of data pits or groove tracks with concave and convex shapes. Next, repeat the above method for forming the first recording layer to form a second recording layer on the gap layer. Finally, a polycarbonate protective layer is formed on the second recording layer.

In summary, the optical recording medium with three-dimensional data graphics of the present invention has higher quantum efficiency and stoke shift (stoke shift) due to the low polymerization degree fluorescent material used in it. When the optical recording medium is read by light, the fluorescent material with a low degree of polymerization can be excited to emit fluorescent signals with sufficient intensity, so it has relatively high recording sensitivity and high carrier-to-noise ratio (CNR) value. In addition, the fluorescent material with a low degree of polymerization of the present invention can be dissolved in organic solvents such as alcohols, ketones, esters, ethers, halogen compounds, or amides, so it can be coated by simple coating methods (such as spraying, rolling coating, etc.) Cloth, impregnation, or spin coating, etc.), it can be coated on the substrate. In this way, the manufacturing process of the prior art can be greatly simplified to obtain an optical recording medium with high storage capacity, low cost and high reliability.

The preferred embodiments of the present invention are described above, but they are not intended to limit the present invention. Modifications and changes to the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.

Claims (28)

1. An optical recording medium with three-dimensional data graphics, comprising: a substrate; A plurality of recording layers formed on the first surface of the substrate, the recording layer comprising a fluorescent material with a low degree of polymerization having a structure of formula I, _ZXn Formula I Where n is 2 to 10; Z is

or

X is

or Y is S, O or

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different substituents, which are hydrogen atoms, alkyl groups, alkyl ester groups or alkoxy groups, wherein the alkyl, alkyl The ester group or alkoxy group contains 1-20 carbon atoms, which is a straight chain or branched chain, and the hydrogen on one or more carbons of the above-mentioned low-polymerization fluorescent material with the structure of formula I can be replaced by a halogen atom . 2. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein each recording layer is separated by a gap layer. 3. The optical recording medium with three-dimensional data graphics as claimed in claim 2, wherein the gap layer is a light-transmitting adhesive layer or a polymer layer. 4. The optical recording medium with three-dimensional data graphics as claimed in claim 2, further comprising a protective layer covering the uppermost recording layer. 5. The optical recording medium with three-dimensional data graphics as claimed in claim 4, wherein the refractive index of the substrate, the recording layer, the gap layer and the protective layer are substantially the same. 6. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the recording layer has a plurality of data pits, the data pits are dispersed in the recording layer, and the low-polymerization fluorescent material is filled into the plurality of data pits in the pit. 7. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the Stoke shift of the fluorescent material with a low degree of polymerization is not less than 50 nm. 8. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the molecular weight of the low-polymerization fluorescent material is between 500 and 4500. 9. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the quantum efficiency of the fluorescent material with a low degree of polymerization is not less than 0.02Φ. 10. The optical recording medium with three-dimensional data graphics as claimed in claim 9, wherein the quantum efficiency of the low-polymerization fluorescent material is not less than 0.1Φ. 11. The optical recording medium having a three-dimensional data pattern as claimed in claim 1, wherein n is 3-6. 12. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein there is a second surface on the opposite side of the first surface of the substrate, and there are a plurality of recording layers on the second surface. 13. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the optical recording medium is a read-only optical disc. 14. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the optical recording medium is a write-once optical disc. 15. The optical recording medium with three-dimensional data graphics as claimed in claim 1, wherein the optical recording medium is read by a blue-ray laser. 16. A method of manufacturing an optical recording medium having a three-dimensional data pattern, comprising: providing a substrate; A plurality of recording layers are formed on the first surface of the substrate, and the recording layers include a fluorescent material with a low degree of polymerization having a structure of formula I, -(-ZX-) _n - Formula (I) Where n is 2 to 10; Z is

or

X is

or

Y is S, O or

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different substituents, which are hydrogen atoms, alkyl groups, alkyl ester groups or alkoxy groups, wherein the alkyl, The alkyl ester group or alkoxy group contains 1-20 carbon atoms, which is a straight chain or a branched chain. The hydrogen on one or more carbons of the above-mentioned low-polymerization fluorescent material with the structure of formula I can be replaced by a halogen atom. replace. 17. The method of manufacturing an optical recording medium having a three-dimensional data pattern as claimed in claim 16, comprising forming a gap layer between each recording layer to separate adjacent recording layers. 18. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 17, further comprising covering and forming a protective layer on the uppermost recording layer after the recording layer and the gap layer are completed. 19. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 18, wherein the refractive indices of the substrate, recording layer, gap layer and protective layer are substantially the same. 20. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the recording layer is dispersed with a plurality of data pits, and the low-polymerization fluorescent material is filled in the plurality of data pits. 21. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the fluorescent material with a low degree of polymerization is dissolved in a solvent and formed in the plurality of data pits. 22. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the Stokes shift of the low-polymerization fluorescent material is not less than 50 nm. 23. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the molecular weight of the fluorescent material with a low degree of polymerization is between 500 and 4500. 24. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the quantum efficiency of the fluorescent material with a low degree of polymerization is not less than 0.02Φ. 25. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 24, wherein the quantum efficiency of the low-polymerization fluorescent material is not less than 0.1Φ. 26. The method of manufacturing an optical recording medium having a three-dimensional data pattern as claimed in claim 16, wherein n is 3-6. 27. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the optical recording medium is a read-only optical disc. 28. The method for manufacturing an optical recording medium with three-dimensional data graphics as claimed in claim 16, wherein the optical recording medium is a write-once optical disc.

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