TW569201B - Optical recording medium and method for manufacturing it - Google Patents

Abstract

A recording medium for an optical data storage means of the DVD-R-type writable and readable with a laser beam of a wavelength of 630 to 680 nm, contains for the absorption of the laser energy a subphthalocyanine (sPcY). The sPcY is present in the recording medium partly as an ion complex with a bis- or triphenolate or a bis- or trithiophenolate (bPh or tPh) and partly as an ion complex with an anionic metal thiolene complex or a metal diazo complex (MC). The ion complexes have the following structures, wherein: sPcY-, sPcY'-, sPcY""- and sPcY'""- are equal or different. The recording medium exhibits a very high stability and is writable with very high writing speeds.

Description

569201 A7 B7 V. Description of the invention (1) (Please read the notes on the back before filling this page) The present invention is located in the field of optical data storage devices, and is related to the optical recording medium and its basis according to the preamble of the first independent application. Method for manufacturing optical recording medium in corresponding independent application preamble. The known optical data storage device includes a disc-like substrate of transparent plastic, a recording layer deposited on the substrate, and a reflective layer deposited on the recording layer. A spiral recording groove in which a recording layer is deposited is included on the other side of the substrate. The data is stored in such a manner that laser light with a write light function is written along the groove, wherein the recording layer has a local change and pit-like bubbles are formed between the recording layer and the substrate. The written track is scanned with another laser light having a reading light effect, in which the reading light reflected on the reflective layer is recorded as a reading signal. The optical data storage device of DVD-R type (recordable digital versatile disc) is different from the optical data storage device of CD-R type (recordable optical disc) in that the recording grooves are closer to each other and the disc often contains two A half substrate with a recording layer and a reflective layer arranged therebetween. DVD-R (CD-R: 780 nm) was printed with laser light with a wavelength of 630 to 680 nm for writing and reading. A suitable recording layer is composed of a recording medium that absorbs laser energy and includes, for example, a phthalocyanine-boron compound having the following general formula:

This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 569201 A7 B7 V. Description of invention (2) (Please read the notes on the back before filling this page) where A 1 to A 1 2 are separate from each other Is Η'-halogen, -alkyl, -aryl, monoalkylaryl, oxyalkyl, oxyaryl, -oxyalkyl-aryl, -thioalkyl, -sulfur Substituted aryl or -thioalkyl-aryl, wherein the alkyl group has 1 to 20 carbon atoms and the aryl is phenyl or naphthyl or a halogen derivative thereof, and wherein fluorene is boron. X is halogen, 10H, 10C2H5, or 10-tert-butyl, as exemplified in the publication US-5 7 7 6 6 5. In the same publication, it is suggested that X is phenyl or phenoxy, which is preferably unsubstituted. In a known manner, the recording layer 尙 includes, for example, a photoinhibitor in the form of a metal complex (e.g., a metal sulfene complex) and a stabilizer (e.g., an amine) when appropriate. The purpose of printing the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics is to provide an optical data storage device that can read and write with a laser having a wavelength between 630 to 680 nm (for example, DVD-R) can be used as a recording medium, which can write to this recording medium mainly based on phthalocyanine at a very high speed (especially low and suitable writing energy), and has a particularly high resistance to light and weather. The recording medium is distinguished from these known recording media by the fact that the recording layer of the recording medium according to the present invention is stable. Moreover, the object of the present invention is to create a new method for manufacturing a recording medium. These objectives are achieved with a recording medium as defined in the scope of the patent application and its manufacturing method. The recording medium according to the present invention includes a phthalocyanine having a boron or aluminum as a central atom as a laser energy absorbing compound. The phthalocyanine system in the recording medium according to the present invention exists in the form of ionic complexes, especially the -------- _ This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 569201 Α7 Β7 V. Description of the invention (3) (Please read the notes on the back before filling out this page) The copy consists of two or three phthalocyanine units (s P c Y-) and bisone or triphenolate Or bis- or trithiophenate (b P h — or> t P h-) composed of ionic complexes and a part of which is composed of a phthalocyanine unit (s P c γ-) and anionic metal sulfur An ionic complex consisting of a complex or a metal diazo complex (MC) exists. The recording medium according to the invention therefore includes the following ionic complexes: sPcY-bPh-YsPc1 or sPCY-tPh-YsPc,

I

YsPc "

And sPcY, " -MC where: sPcY, spcY,, sPcY "and s P c Y are the same or different and have the following general structure:

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ where A1 to A1 2 are independently Η, —halogen, —alkyl, —square, one-base —aryl, —oxyfluorenyl, —oxyaryl , An oxygen-containing group, an aryl group, -thioalkyl, -thioaryl, or -thioalkyl-aryl 'wherein the alkyl group has 1 to 20 carbon atoms and the aryl group is phenyl or naphthalene Group or its halogen derivative, and its intermediate is boron or aluminum; this paper size applies Chinese National Standard (CNS) M specification (21〇 > < 297) 569201 A7 B7 V. Description of the invention (4) where b P h and t P h have the following general structure:

(Please read the precautions on the back before filling out this page) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed nothing in position Z, there was a C Η 2-, —C2H4 —, one S —, one 10 —or ΝΗ—and a (CnH (2n-1)) < (with η = 1, 2 or 3)-or a N < at the position Z ', and each of the benzene rings except one __ or one S -In addition, it carries up to 2 additional substituents R1 to R6, wherein R1 to R6 are each independently a halogen, a CN, a NO, an -alkyl group, an aryl group, -Oxygen radical, -oxygen radical, -oxygen radical -square radical, -thiogen radical, -thioaryl radical, -thio radical -aryl radical, -S 0 3 Η >- S 0 2 Η >-S 0 3 Ν (alkyl) 2, -NΗ2, -NΗ (alkyl), -NΗ (aryl), -N (alkyl) 2, -N (aryl) 2, Wherein the alkyl group has 1 to 8 carbon atoms and the aryl group is -phenyl or -naphthyl or its substituted derivative; wherein the MC is a metal sulfene complex or a metal diazo complex having the following general structure Property: This paper size applies Chinese national standard ( CNS) A4 specification (210 × 297 mm) 569201 A7 B7 V. Description of the invention (5

XS Μ 5ya ~ ^

Where M = Ni, Co, Fe, Cu, Sn, Zn, (please read the precautions on the back before filling this page) Printed by A1, Ti, Ti〇, Cr, V, V〇, Pt, Pd,

Ge or Si, and each benzene ring carries up to 2 substituents R '1 to R' 8, among which 11 '1 to R' 8 are each independently —halogen, —NOS'—NH2, —NH ( Alkyl), NH (aryl), N (alkyl) 2, N (aryl) 2, —CN, —oxyalkyl, —oxyaryl, —thioalkyl, —thioaryl Group, in which the alkyl group has 1 to 8 carbon atoms and the aryl group is -phenyl or -naphthyl or a substituted derivative thereof. _ ^ _ 8 _ = _ This paper size applies Chinese National Standard (CNS) A4 (210X 297mm) 569201 A7 ___B7_ 5. Description of the invention (6) (Please read the precautions on the back before filling this page) All of the phthalocyanine units present in the recording medium of the present invention are substituted in the same manner and have the same central atom Y (boron or aluminum), or they are substituted in different ways and have different central atoms Y. In all the phthalocyanine units, the substituents A 1 to A 4 are preferably the same as the substituents A 5 to A 8 and the same as the substituents A 9 to A 12. Preferred examples of phthalocyanine have the following substituents: A1 to A12 = — Η (unsubstituted sPcY); A1, A4, A5, A8, A9, A12 = —octyl and A2, A3, A6, A7, A10, A11 = — Η; A2, A3, A6, A7, A10, A11 = —Octyl and A1, A4, A5, A8, A9, A12 = _H; A2 or A3, A6 or A7, A10 or A1 1 = -octyl and all others = one; A2, A 6, A 1 〇 = —phenoxy and all others = —Η; A1, A5, A9 = —thiophenoxy and others all = one Η y A1, A5, A9 = —Oxygenyl, A3, A7, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A 1 1 =-C 1 can exist as bis- or triphenate or bis- or trithiophenate In the recording medium according to the present invention, or as a mixture of various of these phenates. Also in each phenate, the substituents R 1 / R 2 are preferably the same as the substituents R 3 / R4 and R5 / R6. The preferred examples of bis- or triphenate or -thiophenate are the anions of the following phenols:--Q. This paper size applies to China National Standard (CNS) A4 (210X297 mm) ~-569201

2 2, 2, 2, 4, 4.4, 2, 2, 2, 2 Methylbis (6-tert-butyl-4 4-cresol) Methylbis (6-Terbutyl-4 ~ ethylphenol) Methylbis (6 4,6-xylenol), isobutylidene bis (4,6 methylenediphenol) 4-methyl-6-α-cyclohexylphenol 4-methylidene bis (2,6_dibutylphenol) , Butylidene 3 ^ (6-tert-butyl-3-carboxylic acid), monothiobis (6-tert-butyl-4-methylphenol), monothiobis (4-methyl-6-α-methyl) Benzene (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2,2, —Thiobis (4,6 1,2 dipentaphenol), 4, 4, 1 Thiobis (6-tert-butyl-2 ~ cresol), bis (4-hydroxy ~ 3,5-ditert-butylbenzyl) sulfide, 2'2 'mono-bis (5-diethylaminophenol) ), 4,4 —monoethyl-6,6, —di-tert-butyl-2,2, —bisphenol, 4,4, —diethyl-6,6, —ditert-butyl-2,2 — Bisphenol, 1,1,3-tris (5, -tert-butyl-4, -hydroxy-2,1-tolyl) butane. Preferred anionic metal thiophene And metal complexes thereof as diazo paper of the present scale applies China National Standard (CNS) Α4 size (210x297 Dong well) -in - 569201 Α7 Β7 V. invention is described in (8)

no2 is between ionic complex (s P c Y) 2 — b P h or (spc Y) 3-t P h (Ionic complex of phthalocyanine with bis- or tri-phenate or mono-thiophenate ) And ionic complex s P c Y — MC (the ionic complex of phthalocyanine and anionic metal sulfene or metal diazo complex) is between 1: 9 9 to 9 9: 1. In addition to the phthalocyanine ion complex, the recording medium may include cyanine, styri 1, fomaza η, diazo and / or metalized diazo dyes as more laser energy absorbing compounds . In addition, it may also include up to 10 parts by weight of a metallocene (for example, ferrocene), an acetamidine pyruvate metal complex, and Ν, N'-tetraalkyl (or monoaryl) substituted p-diaminobenzene and / or oxoline. The production of phthalocyanine with boron or aluminum as the central atom is made by appropriately substituted 1,2-dicyanobenzene (/ phthalonitrile) and boron halide or aluminum (preferably boron trichloride or trichloride Aluminum) reaction. 1,8-diazinebicyclo [5 · 4 .〇]-7-dodecene (DBU) was used as the catalyst (preferably the ear-to-earth ratio of acetonitrile was from 0.1 · 2 to 1.2). Based on this reaction, the paper size applies the Chinese National Standard (CNS) Α4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) A7 B7 5. Description of the invention (9) Production of halogenated phthalocyanine. (Please read the notes on the back before filling this page) Put the halogenated phthalocyanine in a suitable organic solvent or solvent mixture on the one hand with an excess of bis- or triphenate and on the other hand with an excess of anionic metal sulfur Ethylene complexes or metal diazo complexes (preferably in about a 5-fold excess) are dissolved and stirred at elevated temperatures for a longer period of time (for example, at 5 to 100 ° C over 5 to 50 hours). The water-soluble salt is then washed with water, and the organic ion complex is separated, washed, recrystallized or purified in another suitable manner and dried. Regarding the production of the recording layer, the phthalocyanine ion complexes of the respective recording media were dissolved in an organic solvent with more compounds in a predetermined ratio as appropriate. A solution of the recording medium is deposited, for example, on a polycarbonate substrate by spin coating and then dried. When a recording medium is produced in this manner, a reflective layer of silver, gold, or aluminum or an alloy of these metals is deposited, for example, by sputtering. When appropriate, it is covered with a protective lacquer coating, and the disc produced in this manner is fixed to the second substrate, which also has a protective lacquer coating, as an adhesive layer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 1: Synthesis of unsubstituted phthalocyanine-boron compounds will dry 1,2-dicyanobenzene (0.5 g, 0. 〇4 mol ) Suspended in freshly distilled chlorobenzene (12 ml) with DBU (0.02 mol) under nitrogen. The suspension was cooled to a temperature of 3 ° C, and 20.5 ml of a 1 mol of boron trichloride (B C 1 3) solution in n-hexane was slowly added via a syringe. The yellow-green solid is heated slowly to 60 ° C with strong agitation, where the fluid will turn black. Hexane was distilled. Then hold 12 paper standards to apply Chinese National Standard (CNS) A4 specifications (21〇X 297 public directors) 569201 A7 ___ B7 V. Description of invention (10) (Please read the precautions on the back before filling this page) Continued on 1 Stir for another 10 minutes at 0 ° C. The color changed to violet. The liquid phase was removed and the solid was first extracted with petroleum ether (80-100 ° C) and then extracted with toluene for 2 hours. The residual brown solid was recrystallized from ethanol, washed with petroleum ether and sublimed at 350 t. The result is 3. 57 g (64%) of a brown powder-like product: UV (DMF) Amax: 562,302 nm; IR (KBr): 1692, 1611, 1452, 1384, 1280, 119 5, 1130, 950, 878, 753, 695, 629 cm XHNMR (360MHz) (DMS Ο-d 6): 58.85 (6H, dd), 7. 9 0 (6 Η >dd); MS (EI 7 0 e V, 2 6 0 ° C): m / z464 (M ++ Cl—H, 4), 431 (M +, 20), 430, (55), 429 (18), 396 (70), 267 (10), 256 ( 8), 215 (5), 197.5 (35), 139 (15 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 2: Phthalyanine-aluminum compounds substituted with trithiooctyl (regioisomerization) 5mLchlorochlorobenzene The synthesis of dry 4-thiothiophthalonitrile (460 g, 1.79 mmol) and DBU (1 mmol) were suspended in 0.5 ml of chlorobenzene under argon. Medium. Add 0.15 ml via a tube with a slightly greater pressure than argon. ____ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 569201 A7 _ B7_ V. Description of the invention (彳 1) (Please read the notes on the back before filling out this page) (1.79 Mol) Aluminum chloride (concentrated in advance at 78 ° C). The mixture was then stirred at room temperature for 10 minutes, and then at 80 ° C for 15 minutes. After cooling, the precipitated black solid was mixed with hexane. Rinse, filter, and separate the chromatographic layer with hexane / dichloromethane (1: 1) on A 1 203. This gives 201 g (44%) of a sticky violet compound. Example 3 : Manufacture of ionic complex of phthalocyanine and bisphenolate. 4 '-diethyl-6,6, -di-tert-butyl-2,2' -bisphenolate sodium salt in 5 times excess. The molar amount was added to 0.01% molar 1,4,5,8,9,12-hexaoctyl-s P c -boron bromide solution in 5% in n-butanol. The resulting solution was added at 8 Stir at 0 ° C for 12 hours, cool and then pour into cold water, where the organic components are precipitated and the water-soluble inorganic salts are dissolved. The precipitated solid is filtered, washed with water, recrystallized from ethanol and dried in vacuum. Example 4: Manufacturing an ionic complex of phthalocyanine and dithiophenate. The Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, printed 4,4'-diethyl-6,6'-di-tert-butyl. 2, 2,-Sodium salt of bisphenol is added in a 5-fold excess of phthalocyanine to a 0.01% mole of 2,01,6,10-triphenoxy-sPc-boron bromide solution in chlorobenzene in. The resulting solution was stirred at 80 ° C for 10 hours. The solvent was then distilled and then recrystallized from ethanol and dried in vacuo. Example 5: Manufacture of ionic complex of phthalocyanine and metal diazo complex ------: 14 -______ This paper size applies to China National Standard (CNS) A4 (210X297 mm) 569201 A7 B7 V. Description of the invention (12) (Please read the notes on the back before filling out this page) Di (2—Ethyl-5—nitro-4—1-ethyl heavy gas 酣) —T i〇 (II) — Tetrabutylammonium bromide was added in 5% dimethylformamide / H2O (9 5: 5) 0.001 mole 1 '5' 9 -thiotolyl-s P c-bromination Boron (III) solution. The resulting solution was stirred at 70 ° C. for 12 hours, cooled and poured into cold water. This is followed by the same steps as described in Example 3. Example 6: Production of ionic complex of Asian-European cyanine and metal disulfide complex. Bis-1,2- — (4-methoxybenzo-1,2-dithiocan) —N i (II) — Tetrabutylammonium bromide was added with 5% molformamidine / H2O (95: 5) 0.01 mol 1 '5' 9 -trihexyloxy-3,7,11 trichloro -SPc-B (III) bromide solution. The resulting solution was stirred at 70 ° C for 15 hours', cooled and poured into cold water. Then follow the same steps as explained in Example 3. Example 7: Manufacturing and testing of optical data storage devices Printed by the Consumer Cooperatives of the 4th Bureau of the Ministry of Economic Affairs and the Intellectual Property Bureau. DVD-R data storage devices were manufactured using the phthalocyanine-containing ionic complexes obtained in Examples 3 to 6. Dissolve the phthalocyanine-containing ionic complexes and more compounds, respectively, dissolved in an organic solvent or a solvent-based mixture (e.g., 2, 2, 3) with a predetermined amount in a predetermined amount when appropriate , 3-tetrafluoropropanol, 2-ethoxyethanol, diazetone alcohol / butanol (10: 1), diazetone alcohol / isopropanol (10: 1) or ethyl cellosolve). The solution concentration changes within the range of 0 · 5-5% by weight. ___________ 1 q _ _ This paper size applies to Chinese National Standard (CNS) A4 (210X 297) ~ " 569201 A7 B7 V. Description of the invention (13) Polycarbonate substrate discs required by injection molding (Diameter (please read the notes on the back before filling in this page) 120 mm, thickness 0.6 mm). A groove spiral with a pitch of 0.74 microns was included on one surface of the disc. The groove depth in the 100-200 nm range and the groove width in the 180-400 nm range are selected, depending on the recording medium used. The thickness of the recording layer in the groove changes within the range of 90-140 nm and the thickness of the recording layer on the ground varies within the range of 10-30 nm, which is based on the Depending on the optical parameters of the laser energy absorbing compound. The coated polycarbonate substrate is then dried at 70 to 80 ° C. A reflective gold layer with a thickness of 70-120 nm is deposited by sputtering. A lacquer protective layer (about 4 microns thick) was then deposited and cured under UV irradiation. Polycarbonate discs without a dye or metal layer also have a protective lacquer coating. In each case, the disc having the recording layer, the metal layer, and the lacquer protective layer and the disc having only the lacquer protective layer were bonded together in an adhesive manner using a suitable adhesive. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the same way, a disc with a recording layer of a cyanine dye from Fuji Foto Film Co., Ltd. is manufactured as a standard data storage device. The dye has the following structure:

-. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 569201 A7 B7 V. Description of invention (Μ)

(Please read the notes on the back before filling this page.) The recording layer of the standard disc 尙 contains a photo-suppressant (Q), for example, I RG2 2 of NipponKayako Co., Ltd. The disk manufactured in the above manner was written and tested with laser light using a test device from e-focus Co., Ltd. (wavelength 635 nm; linear writing speed: 3.49 m / s). Then test their light and environmental stability (according to the ISO 1105-B02 standard and basis using air-cooled xenon lamps; TEC68-2-2Ba and JEC68-2-3 0 D d). All data storage devices containing the recording layer of the recording medium according to the invention meet the test standards and also the subsequent light and climate tests. Compared with this technique (according to Ding DK Company's S — printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 1 6 8 8 4 3 and the standard disc with a recording medium mainly composed of methine dyes is the best The test results are summarized in the table below on average. The optical data storage device containing the recording layer of the recording medium according to the present invention can be successfully written and read with laser light having a wavelength of 650 nm. The standard parameters are also obtained in this paper. Computer simulation shows that the recording with the recording medium according to the present invention can also be written at a writing speed greater than 4 X _ --17-_ This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 569201 A7 B7 5. Description of the invention (15) layer of optical data memory. Recording medium according to US61 68843 (TDK Company) 70% C1 + 20% C2 + 10% Q (sPcY) 2bPh or (sPcY) 3-tPh (l) SPcY-metal sulfide complex (2) SPcY-metal diazo (Complex (3) 15% (1) + 85% (2) 5% (1) + 95% (3) 10% (1) + 30% (2) + 60% (3) 30% C1 + 10% (1) + 20% (2) + 40% (3) Standard (Please read the notes on the back before filling this page)-Binding

P Optical writing Amplitude-based reflection jitter (milliwatts) (%) (%) (%) 7.2 60 46 8.0 > 12 · ___ — 7.2 60 50 8.0 7.0 64 48 7.9 6.9 68 47 7.8 6.7 70 48 7.6 6.4 71 47 7.5 6.4 71 48 7.5 6.2 72 46 7.4 6 < 〇SE < 12 > 60 > 45 < 8.0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ______- 1 This paper size applies Chinese national standards ( CNS) A4 size (21 × 297 mm)

Claims (1)

569201 A8 B8 C8 D8 VI. Patent application scope 彳 1 _ A recording medium for optical data storage devices that can write and read laser light with a wavelength of 6 300 to 6 800 nm, absorbs laser light for a while. --- ^^: ...... ^^. The recording medium used for energy includes partly ionic errors with bis- or triphenate or bis- or trithiophenate (b P h or t P h). The compound and part thereof are phthalocyanine (sPcY) existing as an ion complex having an anionic metal sulfene complex or a metal diazo complex (MC). The ion complex has the following structure: sPcY- bPh-YsPc, or sPCY-tPh-YsPc 'I YsPc "and sPcY, " -MC where sPcY —, sPcY' —, sPcY, and — and s P c Y " I — are the same or different, and Has the following structures: Wherein A1 to A1 2 are each independently —fluorene, monohalogen, monoalkyl, —aryl, —denyl—aryl, —oxygenated radical, —oxygenated aryl, —oxyalkylated —aryl. '-Thioalkyl, -thioaryl or -thioalkyl-aryl, in which the alkyl group has 1 to 20 carbon atoms and aryl system-this paper size applies to China's national kneading rate (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-19- 569201 A8 B8 C8 D8 Patent application scope 2 Phenyl or -naphthyl or halogen-substituted derivatives thereof, and wherein Y is boron or aluminum; where b P h and t P h has the following general structure: bPh: tPh: (Please read the precautions on the back before filling out this page) The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed nothing in position Z, with -C Η 2-, —C2H4 —, — S —, — ◦— Or —NΗ — 'and at position Z has — (CnH (2n-i)) < (with η = 1, 2 or 3) —or an N <, and each of the benzene rings except -0- or- S- also carries up to 2 additional substituents R1 to R6, where R1 to R6 are the same. This alone is -halogen, -CN, -N02, -alkyl, -aryl, -alkyl -Aryl, -oxyalkyl, -oxyaryl, -oxyalkyl-monoaryl, monothioalkyl, -thioaryl, -thioalkyl-aryl, -S. 3H, -S02H, -S03N (alkyl) 2,. -NH2, -NΗ (alkyl), -NΗ (aryl), -N (alkyl) 2,-N (aryl) 2 , Where the alkyl group has 1 to 8 carbon atoms and the aryl group is -phenyl or -naphthyl or its substituted derivative; this paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)- 20- 569201 A8 B8 C8 D8 VI. Scope of benefits 3 Among which, M C is a metal sulfene complex or metal diazo complex having the following general structure: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling out this page) A1, Ti, Ti〇, Cr, V, V〇, Pt, Pd, G e, or Si, each of which carries up to 2 substituents R'1 to R'8, of which '1 To R '· 8 series are each independently —halogen, —N02, —NH2, —NH (alkyl), —NH (aryl), —N (alkyl) 2, —N (aryl) 2, A CN, an oxyalkyl group, an oxyaryl group, a thioalkyl group, a thioaryl group, and the alkyl group mentioned therein have 1 to 8 carbon atoms and the aryl system mentioned -Phenyl or this paper size applies Chinese national standard (CNS> A4 specification (210X297 mm). 91-'569201 Printed by A8, B8, C8, D8, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application 4-Naphthyl or Derivatives which are substituted. 2. The recording medium according to item 1 of the scope of patent application, which is characterized by "------- ^ ionic complexes containing bis- or triphenate or -thiophenate The molar ratio of the ionic complex to the ionic complex containing an anionic metal sulfur-fired complex or a metal diazo complex is between 1:99 to 9.9: 1. 3. If applying for a patent In the range il or 2 items, The recording medium of one item is characterized in that the phthalocyanine has at least partly equal substituents A 1, A4, A5, A8, A9 and A12 and equivalent A2, A3, A6, A7, A10 and All. 4 · For example, the recording medium v in any one of the "1 or 2 scope of the patent application" is characterized in that the substituents R1 and R2 in the bis- or tri-phenate or -thiophenate are the same as the substituents R3 and R4 It is the same as the substituents R5 and R 6. 5. The recording medium according to any one of the scope of patent application # 1 or 2, characterized in that it is a substituent in a metal sulfene complex or a metal diazo complex R1, R3, R5, and R7 are completely the same, and the substituents R2, rulers 4, 116, and 118 are completely the same. 6 · As a recording medium in any one of the scope of patent application i 1 or 2, it is characterized in metal sulfene The complex or metal diazo complex has the same substituents in the following ways: R1 / R2 = R7 / R8 and R3 / R4 = R5 / R6. 7. If any of the scope of application for m- The recording medium of one item is characterized in that it includes at least one other compound that absorbs laser energy in addition to phthalocyanine. Zhang scale is applicable to China National Standards (CNS) A4 (210X297 mm) -22- (Please read the precautions on the back before filling out this page), 11 line 569201 Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative, printed A8 B8 C8 D8A, patent application scope 5 8. The recording medium in the scope of patent application item 7 is characterized in that another laser energy absorbing compound is cyanine dye, stydl dye, formalin dye, diazo dye or metallized heavy Nitrogen dye. 9. The recording medium of item te- in item 1 or 2 of the scope of application for a patent, characterized in that it comprises metallocene, acetamidine pyruvate metal complex, and p-diamine group substituted with N, N 'one to four. Phenol and / or quinoline. 1 0. A DVD-R type data storage device having a transparent plastic substrate, a reflective layer, and a recording layer arranged between the substrate and the reflective layer, characterized in that the recording layer is composed of records such as the first item in the scope of patent application Composed of media. 11. The data storage device according to item 10 of the patent application scope, characterized in that a second transparent plastic layer is provided on a reflective layer facing away from the recording layer. 12. The data storage device according to item 11 of the scope of patent application, which is characterized in that the reflective layer and the second plastic layer each carry a lacquer protective layer, and the lacquer protective layers are bonded to each other with an adhesive. 13. The data storage device according to any one of claims 0 to 12 in the scope of the patent application, characterized in that the reflective layer is composed of gold, silver, aluminum or gold, silver or aluminum alloy. 1 4 · A method for manufacturing a recording medium such as the item 1 in the scope of patent application, which is characterized by individually synthesizing, purifying, and drying an ionic complex of the recording medium, and then dissolving it in an organic solvent in a predetermined amount ratio. 1 5 · The method according to item 14 of the scope of patent application, which is characterized by using halogenated phthalocyanine and excess bis- or tri-phenate or -thiophenate or over (please read the precautions on the back before filling (This page)-The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210 × 297 mm) -23- 569201 A8 B8 C8 D8 VI. Patent application scope 6 amount of metal sulfur complex or metal diazo The complex is reacted to synthesize an ionic complex. 1 6 _ The method according to item 5 of the patent application, characterized in that the excess is a 5-fold molar excess. 17. The method according to any one of the 15th or 16th of the patent scope of claim I is characterized in that it is between 60 and 100. The ionic complex is synthesized by stirring the reactant mixture for 5 to 50 hours at a temperature of: (1) The method according to any one of items 15 or 16 in the patent scope of claim g, characterized in that The reaction of phthalonitrile with boron halide or aluminum aluminide in the presence of 1,8-diazine bicyclo [5.4.0] -7-dodecene (DBU) to synthesize halophthalocyanine. 1 9 · If a patent The method in the range of item 18 is characterized by the use of DBU with a molar ratio of 0.1: 2 to 1: 2 (please read the precautions on the back before filling out this page). Printed on paper by the Consumers' Cooperative of the Ministry of Intellectual Property Bureau of the People's Republic of China, using China National Car (CNS) A4 (210X297 mm) -24-