CN101166632A - Optical recording medium, and optical recording method and optical recording apparatus thereof - Google Patents
Optical recording medium, and optical recording method and optical recording apparatus thereof Download PDFInfo
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- CN101166632A CN101166632A CNA2006800096972A CN200680009697A CN101166632A CN 101166632 A CN101166632 A CN 101166632A CN A2006800096972 A CNA2006800096972 A CN A2006800096972A CN 200680009697 A CN200680009697 A CN 200680009697A CN 101166632 A CN101166632 A CN 101166632A
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Abstract
The present invention provides an optical recording medium including a substrate and a recording layer on the substrate having a squarylium metal chelate compound with a central metal. The recording layer includes a mixture of squarylium metal chelate compounds having ligands of the same type as well as metals of two or more types as the central metal. It is preferable that the recording layer includes a squarylium metal chelate compound having a bivalent metal as its central metal and a squarylium metal chelate compound having a metal other than a bivalent metal as its central metal.
Description
Technical field
The present invention relates to a kind of jumbo optical recording media, be particularly related to a kind of optical recording media with recording layer of the side's of containing acid (squarylium) metal-chelate combination compound, wherein pass through illumination beam, can write down, reproduce and add information, the invention still further relates to the optic recording method and the optical recorder that wherein use described optical recording media.
Background technology
At present, promoted exploitation as primary writing in multi-time reading out type (write-once-read-many) dvd media of huge capacity compact discs.As the basic fundamental that improves recording capacity, to the exploitation of the recording materials that make record pit (recording pit) microminiaturization, to introduce with MPEG2 be the image compression technology of representative and to be used for the relevant technological development of the wavelength of semiconductor laser in reading and recording hole with shortening be necessary.
At the technical elements that shortens wavelength, only there is the AlGalnP semiconductor laser in the red wavelength zone bar code reader and measuring instrument to be realized commercialization up to now with the 670nm wave band, but along with the continuous increase of CD density, red laser beam enlarges in the use that light stores on the market.
Aspect the DVD driving, the standard of wavelength of the semiconductor laser in the 630nm-690nm wave band is turned to light source.In addition, business-like only used again DVD-ROM drives the wavelength with about 650nm.
On the other hand, aspect recording materials, dyestuff such as cyanine dyes and phthalocyanine dye are known to can be used for CD-R (primary writing in multi-time reading out type compact disk), but these dyestuffs are not owing to can not be used for DVD-R (primary writing in multi-time reading out type digital universal disc) corresponding to the absorption edge (absorption edge) of employed red laser beam short wavelength regions in its optical absorption spectra.Therefore, need a kind of can be at the 630nm-690nm wavelength, i.e. the medium that concerning the primary writing in multi-time reading out type dvd media, writes down and reproduce under the most preferred wavelength.
For this technical need, proposed to be used for the various materials of recording layer so far, for example methine dyes (for example patent documentation 1), cyanine dyes and azo-metal chelate dye becomes salt dyestuff (for example patent documentation 2), azo dyes (for example patent documentation 3 and 4), first
Dyestuff (for example patent documentation 5), tetraazatetradecane porphyrin dyestuff (patent documentation 6), two pyrroles's methylene dyes (for example patent documentation 7) and styryl dye.
On the other hand, the applicant of present patent application is devoted to the sour compound in the side that has maximum absorption wavelength under the 550nm-650nm or its metal chelate compound as the medium that can carry out record under the 630nm-690nm wavelength thereon and reproduce, and has proposed to comprise the optical recording media (for example patent documentation 8-14) of these components.
According to their research, can obtain a kind of optical recording media, particularly recording wavelength is had less dependent optical recording media, wherein said optical recording media is because its optical characteristics can be applicable to use vibration wavelength to compare the primary writing in multi-time reading out type dvd media of the semiconductor laser in short wavelength zone more with conventional optical recording media.
In that dye materials is used as in the recording materials of primary writing in multi-time reading out type dvd media, might control optical characteristics more accurately and good primary writing in multi-time reading out type dvd media is provided by the dye materials that mixes two or more.
Yet, when the sour metal chelate compound of two or more sides with different ligands mixes and rests in the organic solvent for a long time, chelate part confusion (scrambling) can take place, thereby form isomers.Usually the optical recording media that includes the organic dyestuff that is used for recording layer in manufacturing, in order to reduce cost, the material of in most of the cases wanting recovery and reuse in the process of coating organic dye material, to be scattered by spin-coating method.Utilize again this, will have different metal and mix, and part that ought be separately is not simultaneously as the sour metal chelate compound of two or more sides of metal, thus because the problem that the exchange of part exists the concentration determination of dyestuff to become difficult.
Patent documentation 4 JP-A No.2000-127625
Patent documentation 7 JP-A No.10-226172
Patent documentation 8 international open No.WO01/044233
Patent documentation 9 international open No.WO01/044375
Patent documentation 11 JP-A No.2002-370451
Patent documentation 12 JP-A No.2002-370454
Patent documentation 13 JP-A No.2004-42624
Patent documentation 14 international open No.WO02/050190
Summary of the invention
The purpose of this invention is to provide: the optical recording media of the recording layer that a kind of mixture that comprises by the sour metal chelate compound of multiple side forms, even this optical recording media also is stable after storing or reusing and can carries out concentration determination by the other side's acid metal chelate compound long-time, wherein said optical recording media have further raising light resistance and applicable to the sour compound in the side of routine and the formed medium of its aluminium chelate compound mutually specific energy accurately control the primary writing in multi-time reading out type dvd media of its optical characteristics; The optic recording method and the optical recorder that use this optical recording media also are provided.
The mode that addresses the above problem is as follows.
＜1〉a kind of optical recording media comprises the recording layer of the sour metal chelate compound in the substrate and the side of having, and wherein said recording layer comprises the mixture of the sour metal chelate compound in the side with two or more different metals.
＜2〉according to＜1〉described optical recording media, wherein said recording layer comprises having divalent metal as the sour metal chelate compound in the side of its metal with have metal except that divalent metal as the sour metal chelate compound in the side of its metal.
＜3〉according to＜1〉to＜2 in each described optical recording media, the sour metal chelate compound of wherein said side comprises identical part.
＜4〉according to＜1〉to＜3 in each described optical recording media, the sour metal chelate compound of wherein said side is represented by following general formula (I):
... general formula (I)
Wherein, in general formula (I), R
1And R
2Can be identical or different, and represent hydrogen atom, can have substituent aliphatic group, can have substituent aralkyl, can have substituent aryl and maybe can have substituent heterocyclic radical; The M representative has the metallic atom of coordination; M represents integer 2 or 3; The X representative can have substituent aryl, can have substituent heterocyclic radical or [Z
1=CH-], Z wherein
1Representative can have substituent heterocyclic radical.
＜5〉according to＜3〉described optical recording media, the X in its formula of (I) is represented by following general formula (II):
Wherein, in general formula (II), R
3And R
4Can be identical or different, and representative can have substituent aliphatic group or form with adjacent carbon atom and can have substituent alicyclic ring and maybe can have substituent heterocycle; R
5Represent hydrogen atom, can have substituent aliphatic group, can have substituent aralkyl, maybe can have substituent aryl; R
6To R
9Can be identical or different, and represent hydrogen atom, halogen atom, can have substituent aliphatic group, can have substituent aralkyl, can have substituent aryl, nitro, cyano group and maybe can have substituent alkoxyl; And R
6To R
9In two functional groups adjacent each other can combine with two adjacent separately carbon atoms to form and can have substituent ring.
＜6〉according to＜1〉to＜5 in each described optical recording media, wherein said central metal is the metal that is selected from aluminium, nickel, copper and zinc.
＜7〉according to＜2〉to＜6 in each described optical recording media, wherein said divalent metal is any at least metal that is selected from nickel, copper and the zinc.
＜8〉according to＜2〉to＜7 in each described optical recording media, the wherein said metal that has except that divalent metal is the trivalent aluminium chelate compound as the sour metal chelate compound in the side of its central metal.
＜9〉according to＜1〉to＜8 in each described optical recording media, wherein said recording layer further comprises and is selected from azo-metal chelate dye, first
At least a metal chelate dye in metal chelate dye and the two pyrroles's methylene metal chelate dyes.
＜10〉according to＜9〉described optical recording media, the metal of wherein said metal chelate dye is at least a metal that is selected from nickel, copper, cobalt, manganese and the oxidation alum.
＜11〉according to＜1〉to＜10 in each described optical recording media, wherein with respect to light with record and playback wavelength ± 5nm wavelength, refractive index n as the described recording layer of individual layer is 1.5≤n≤3.0, and extinction coefficient k is 0.02≤k≤0.3.
＜12〉according to＜1〉to＜11 in each described optical recording media, wherein said recording medium comprises the reflecting layer, described reflecting layer is any in the alloy of gold, silver, copper, aluminium and these metals.
＜13〉according to＜1〉to＜12 in each described optical recording media, wherein said optical recording media is 0.7 μ m-0.8 μ m in suprabasil track pitch, well width is 0.18 μ m-0.40 μ m.
＜14〉according to＜1〉to＜13 in each described optical recording media, wherein record is possible under the 600nm-720nm recording wavelength.
＜15〉a kind of optic recording method, this method under the 600nm-720nm wavelength according to＜1 to＜14 in implement record in each described optical recording media.
＜16〉a kind of optical recorder that wherein has recording medium, wherein said optical recorder is by implementing record and reproducing to described recording medium irradiates light; And described recording medium is according to＜1〉to＜14 in each described optical recording media.
Description of drawings
Figure 1A is the cross sectional representation that shows the layer composition example of optical recording media of the present invention;
Figure 1B is the cross sectional representation that shows the layer composition example of optical recording media of the present invention;
Fig. 1 C is the cross sectional representation that shows the layer composition example of optical recording media of the present invention;
Fig. 1 D is the cross sectional representation that shows the layer composition example of optical recording media of the present invention;
Fig. 2 A is the cross sectional representation that shows layer another example of forming of optical recording media of the present invention;
Fig. 2 B is the cross sectional representation that shows layer another example of forming of optical recording media of the present invention;
Fig. 2 C is the cross sectional representation that shows layer another example of forming of optical recording media of the present invention;
Fig. 3 A is the cross sectional representation that shows layer another example of forming of optical recording media of the present invention;
Fig. 3 B is the cross sectional representation of an example again that shows the layer composition of optical recording media of the present invention;
Fig. 3 C is the cross sectional representation of an example again that shows the layer composition of optical recording media of the present invention;
Fig. 4 is the liquid chromatogram of the solution that wherein is dissolved with the side's sour metallo-chelate mixture among the embodiment 1 (dissolving back just);
Fig. 5 is the liquid chromatogram of the solution (dissolving back just) of the solution (placing after 14 days) that wherein is dissolved with the side's sour metallo-chelate mixture among the embodiment 1;
Fig. 6 is the liquid chromatogram that wherein is dissolved with the solution (just having dissolved the back) of the hungry metallo-chelate mixture of side's acid in the comparative example 1; With
Fig. 7 is the liquid chromatogram that wherein is dissolved with the solution (after 14 days) of the side's sour metallo-chelate mixture in the comparative example 1.
The specific embodiment
(optical recording media)
Optical recording media of the present invention has the recording layer of the sour metal chelate compound in the side of comprising in substrate and the substrate, and it further has other layer as required.
Described recording layer comprises the sour metal-chelate combination of the side with two or more different metals compound.The sour compound in this side and have the conventional sour compound in side and compare with the optical recording media of its aluminium chelate compound and improved tolerance (resistance) with routine, and in duplicate record and reproduction, prevent the light degradation of recording layer.
In addition, preferably described recording layer comprises having divalent metal as the side of its central metal sour metal-chelate combination compound with have other metal except that divalent metal as the side of its central metal sour metal-chelate combination compound.
Therefore, comprise having divalent metal and metal except that this divalent metal respectively as the recording layer of the side of central metal sour metal-chelate combination compound and the sour compound in the side of routine and have the conventional sour compound in side and compare with the optical recording media of its aluminium chelate compound and improved tolerance, and in duplicate record and reproduction, prevent the light degradation of recording layer.
In addition, for record and the reproduction performance that satisfies the primary writing in multi-time reading out type dvd media, for example recording sensitivity and reflectivity are necessary accurately to control the absorbing wavelength of optical characteristics as the dye materials of formation recording materials.It is possible for example controlling optical characteristics by the substituting group of selecting dye materials, but may not be enough.Have divalent metal and the metal except that divalent metal respectively as the sour metal-chelate of the side of the present invention combination compound of its central metal by mixing, might control more accurately.
In addition, the sour metal-chelate combination compound of the side with two or more different metals that is used for recording layer of the present invention preferably has identical part, more preferably has same part.Like this owing to do not form isomers, therefore the recording layer of the present invention of the side's of comprising sour metal-chelate combination compound in solution, store for a long time and repeat to utilize again after do not show the variation that relates to the part confusion.Therefore, possible, for example, the other side's acid metal-chelate combination compound is implemented stable concentration determination and is made high-quality optical recording media effectively.
Optical recording media of the present invention is applicable to so-called primary writing in multi-time reading out type DVD disc system; Therefore, described optical recording media preferably has the recording layer that can carry out optical recording and reproduction by the laser beam of 600nm-720nm record and playback wavelength.Owing to, preferably will be used as recording layer by the mixture that side's sour metal-chelate combination compound of following general formula (I) representative is formed with respect to the optical characteristics of this wave-length coverage:
Wherein, in general formula (I), R
1And R
2Can be identical or different, and represent hydrogen atom, can have substituent aliphatic group, can have substituent aralkyl, can have substituent aryl and maybe can have substituent heterocyclic radical; The M representative has the metallic atom of coordination; M represents integer 2 or 3; The X representative can have substituent aryl, can have substituent heterocyclic radical or [Z
1=CH-], Z wherein
1Representative can have substituent heterocyclic radical.
The example of metallic atom M comprises the metal that is selected from aluminium, iron, cobalt, nickel, manganese, zinc, beryllium, magnesium and calcium in the above general formula (I).Wherein, with regard to optical characteristics and light resistance, preferred aluminium, nickel, copper and zinc.Herein, each part with the central metal coordination is same.
Preferably, the metallic atom M as divalent metal atom is any at least metal that is selected from nickel, copper and the zinc.
The example of the metal except that divalent metal comprises compound such as aluminium, iron, chromium, cobalt, manganese, iridium and vanadium, with regard to optical characteristics, and preferred especially aluminium.
Has this metal as the side of central metal sour metal-chelate combination compound trivalent aluminium huge legendary turtle combination compound preferably.The trivalent aluminium huge legendary turtle combination compound that more preferably has following general formula (III) representative structure:
Wherein, in general formula (III), R
1, R
2Identical with X and above-mentioned definition respectively.
X in the general formula (I) is preferably by the group of following general formula (II) representative:
Wherein, in general formula (II), R
3And R
4Can be identical or different, and representative can have substituent aliphatic group or form alicyclic ring or heterocycle with adjacent carbon atom; R
5Represent hydrogen atom, can have substituent aliphatic group, can have substituent aralkyl and maybe can have substituent aryl; R
6To R
9Can be identical or different, and represent hydrogen atom, halogen atom, can have substituent aliphatic group, can have substituent aralkyl, can have substituent aryl, nitro, cyano group and maybe can have substituent alkoxyl; R
6To R
9In two functional groups adjacent each other can combine with two adjacent separately carbon atoms to form and can have substituent ring.
Further, below each group in the above-mentioned general formula (I) is elaborated.
Aliphatic group comprises alkyl and thiazolinyl.And alkyl and thiazolinyl can be the form of straight chain, side chain or ring.Aliphatic group preferably has the straight or branched of carbon number 1-6, and the ring of carbon number 3-8.
The example of aliphatic group comprises methyl; ethyl; propyl group; isopropyl; butyl; isobutyl group; sec-butyl; the tert-butyl group; amyl group; isopentyl; the 1-methyl butyl; the 2-methyl butyl; tertiary pentyl; hexyl; cyclopropyl; cyclobutyl; cyclopenta; cyclohexyl; suberyl; the ring octyl group; vinyl; pi-allyl; the 1-acrylic; methacryl; crotyl; the 1-cyclobutenyl; the 3-cyclobutenyl; the 2-pentenyl; the 4-pentenyl; the 2-hexenyl; the 5-hexenyl; 2-heptenyl and 2-octenyl.
Moieties in the alkoxyl can be the alkyl of straight chain, side chain or loop type.When alkyl was straight or branched, preferred carbon number was 1-6, and when alkyl was ring, preferred carbon number was 3-8.The example of alkyl comprises methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, hexyl, heptyl, octyl group, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring octyl group.
The preferred carbon number of aralkyl is 7-15, and example comprises benzyl, phenethyl, phenylpropyl and naphthyl.
The preferred carbon number of aryl is 6-18, and example comprises phenyl, naphthyl, anthryl and camomile cyclic group (azulenyl).
The example of halogen atom comprises chlorine atom, bromine atoms, fluorine atom and iodine atom.
And, aralkyl, aryl, alkoxyl, aromatic rings, heterocycle or by R
6-R
9In substituent example in adjacent functional group and their two the formed rings of adjacent carbon atom separately comprise hydroxyl, carboxyl, halogen atom, alkyl, alkoxyl, nitro and can have substituent amino.
The example of halogen atom, alkyl and alkoxyl is same as described above.In the molecule one or more such substituting groups can be arranged.
The substituent example of aliphatic group and alkoxyl comprises hydroxyl, carboxyl, halogen atom and alkoxyl.The example of halogen atom and alkoxyl is same as described above.In the molecule one or more such substituting groups can be arranged.
Amino substituent example comprise 1-2 can be identical or different alkyl, and the example of alkyl is same as described above in this case.
By R
6To R
9In two groups adjacent each other combine formed ring with two adjacent separately carbon atoms and comprise, except carbon number is the aromatic ring of 6-14 such as aliphatic series ring such as the cyclohexane ring that the carbon number the phenyl ring is 3-10.
At general formula (I) with (II), the heterocycle in the heterocyclic group, and by R
3And R
4Example with the formed heterocycle of adjacent carbon atom comprises: five yuan or single six-membered rings aromatics or aliphatic heterocycle containing at least one atom that is selected from nitrogen-atoms, oxygen atom and sulphur atom; And contain ternary to eight yuan condensed ring and at least one and be selected from dicyclo or the tricyclic condensed aromatics or the aliphatic heterocycle of the atom of nitrogen-atoms, oxygen atom and sulphur atom.
The instantiation of heterocycle comprises pyridine ring, the pyrazine ring, pyrimidine ring, the pyridazine ring, the quinoline ring, the isoquinolin ring, the phthalazines ring, the quinazoline ring, quinoxaline ring, the naphthyridines ring, the cinnoline ring, pyrrole ring, the pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, thiphene ring, furan nucleus, thiazole ring, azoles ring, indole ring, the iso-indoles ring, the indazole ring, the benzimidazole ring, the BTA ring, the benzothiazole ring, the benzoxazol ring, purine ring, the carbazole ring, pyrrolidine ring, piperidine ring, piperazine ring, the morpholine ring, the thiomorpholine ring, high piperidines (homopiperidine) ring, high piperazine (homopiperazine) ring, tetrahydro pyridine ring, the tetrahydroquinoline ring, the tetrahydroisoquinoline ring, the oxolane ring, amylene oxide ring, the Dihydrobenzofuranes ring, the tetrahydro carbazole ring.
More than [Z
1=CH-] middle Z
1The example of heterocyclic group comprises indoline-2-base alkene, benzo [e] indoline-2-base alkene, 2-[4-morpholinodithio quinoline base alkene, naphtho-[2,1-d] thiazole-2 (3H)-Ji alkene, naphtho-[1,2-d] thiazole-2 (1H)-Ji alkene, 1,4-EEDQ-4-base alkene, 1,2-EEDQ-2-base alkene, 2,3-dihydro-1H-imidazo [4,5-d] quinoxaline-2-base alkene and 2-benzo seleno azoles quinoline base alkene.
In addition, by R
3And R
4The preferred embodiment of the alicyclic ring that forms with adjacent carbon atom comprises that carbon number is the ring of 3-8, and described ring can be saturated or unsaturated.The example comprises cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclopentene ring, 1,3-cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring.
The compound of above-mentioned general formula (I) representative can be according to the method manufacturing of being set forth among at present known method such as the open No.WO 02/50190 in the world among the present invention.The following describes its manufacture method.
Here, the compound of general formula (I) representative is also referred to as compound (1).In addition, the compound of other chemical formula representative also can be called in a similar manner.
Shown in following reaction scheme (IV), compound (1) is by compound (3) and give metal ion (M
M+) material reaction obtain.
For example, alternatively in the presence of the acetate of 0.5-2 molar part, by with the compound (3) of 1 molar part with (0.5-2)/M of m molar part
M+(giving the material of metal ion) made compound (1) in 1-15 hour in room temperature to 120 a ℃ following reaction in solvent:
Wherein, in reaction scheme (IV), R
1, R
2, M, m and X be with described identical at above-mentioned general formula (1), comprises represented group in the general formula (II).
Give M in the above-mentioned reaction
M+Examples of materials comprise three (acetopyruvic acid) aluminium, three (ethyl acetoacetic acid) aluminium, aluminium isopropoxide, aluminium secondary butylate, aluminium ethylate, aluminium chloride, nickel acetate, acetopyruvic acid nickel, copper chloride, Schweinfurt green, cupric acetylacetonate, zinc chloride, zinc acetate, acetopyruvic acid zinc, beryllium sulfate and acetopyruvic acid magnesium.
The example of reaction dissolvent comprises: halogen solvent such as chloroform and carrene; Arsol such as toluene and dimethylbenzene; Ether solvents such as oxolane, methyl tertiary butyl ether(MTBE); Ester solvent such as ethyl acetate; Alcoholic solvent such as methyl alcohol, ethanol and isopropyl alcohol; And the mixture of these solvents.
Table 1,2 and 3 show corresponding to obtain by above-mentioned reaction and by the ligand moiety except that central metal of the represented sour metal chelate compound in side of general formula (I), promptly corresponding to the instantiation of the part of the middle compound (3) of reaction scheme (IV).
In these examples, the compound number of table among the 1-3 represented the compound number of part, below have this compound as the metal chelate compound of its part by compound number succeeded by its center atom adding with expression.For example, the aluminium chelate compound (complex compound) derived from the sour compd A-1 in side is expressed as A-1-Al.And the compound in the table only is an example, the compound during the sour metal chelate compound of side of the present invention is not limited to show.
Table 1
Table 2
Table 3
In the recording layer of optical recording media of the present invention, except the sour metal chelate compound in side, can also comprise other dye materials.
The example of these dye materials comprises azo dyes, first
Dyestuff, two pyrroles's methylene dyes, methine dyes and azepine cyclenes (azaanulene) dyestuff.Wherein, from the further light resistance of improving, preferred various metal chelate dye materials, preferred especially azo-metal chelate dye, first
Metal chelate dye and two pyrroles's methylene metal chelate dyes.
Herein, by the structure optimization of following general formula (V) representative as the azo dyes in the azo-metal chelate dye.
Wherein, in general formula (V), each Z
2And Z
3All expression forms the part of azo-compound, and representative can have substituent aromatic rings, pyridine residue, pyrimidine residue, pyrazine residue, pyridazine residue, three zin residues, imidazoles residue, thiazole residue, triazole residue, pyrazoles residue, isothiazole residue and benzothiazole residue.
Then, by each several part in conjunction with forming azo-compound, thereby between azo bond, form azo-compound (Z
2And Z
3), and the metal chelate compound of preferred this azo-compound.The metal of this metal chelate compound is a divalent metal atom.
And, first
First in the metal chelate dye
Part is the structure of following general formula (VI) representative:
Wherein, in general formula (VI), Z
4Representative and Z
4The carbon atom of bonding and nitrogen-atoms form the residue of many heterocycles (polyheterocycle) together; A represents alkyl, aralkyl, aryl and cyclohexyl; B represents aryl.
The instantiation of alkyl, aralkyl and aryl is similar to above listed example.
The example that forms the residue of many heterocycles in above-mentioned chemical formula comprises pyridazine ring, pyrimidine ring, pyrazine ring and triazine ring.In addition, this heterocycle can have amino, aryl, aryloxy group and anilino-and the carbonyl of substituting group such as alkyl, alkoxyl, alkylthio group, replacement.In addition, A can have the ester of substituting group such as alkyl, alkoxyl, halogen atom, carbonyl, carboxyl and carboxyl, cyano group and nitro.And B can have the ester of substituting group such as alkyl, alkoxyl, halogen atom, carboxyl and carboxyl, cyano group and nitro.The metal of this metal chelate compound is a divalent metal atom.
The instantiation of the amino of alkyl, alkoxyl, replacement, aryl and halogen atom is similar to above listed example.In addition, alkylthio group is an alkyl and the sulphur group of bonding mutually, and the example of alkyl is similar to above listed group.Aryloxy group is an aryl and the oxygen group of bonding mutually, and the example of aryloxy group is similar to above listed group.
In addition, two pyrroles's methylene moieties in two pyrroles's methylene metal chelate dyes are the represented structure of following general formula (VII):
Wherein, in general formula (VII), each R
10To R
18All represent hydrogen atom, halogen atom independently, can have substituent alkyl, can have substituent alkoxyl, can have substituent thiazolinyl, acyl group, carboxyl or their ester, aralkyl, aryl and heterocycle.
The instantiation of halogen atom, alkyl, alkoxyl, thiazolinyl, aralkyl and aryl is similar to above listed example.In addition, the instantiation of acyl group comprises acetyl group, propiono, bytyry and benzoyl.
When two pyrroles's methylene formed metal chelate compound, metal was a divalent metal atom.
When azo-compound, first
When compound and two pyrroles's methylene compounds formed metal chelate compound, the example of divalent metal atom comprised transition metal such as nickel, copper, cobalt, manganese, oxidation alum, zinc, iron, chromium and aluminium.Wherein, consider the requirement and the dish performance of manufacturing, preferred especially nickel, copper, cobalt, manganese and oxidation alum.
Particularly, for at the record of optical recording media such as primary writing in multi-time reading out type optical recording media and the light in playback wavelength ± 5nm wavelength region may, single recording layer preferably has the refractive index n in the 1.5-3.0 scope, i.e. 1.5≤n≤3.0, and the extinction coefficient k in the 0.02-0.3 scope, i.e. 0.02≤k≤0.3.
Even in record and playback wavelength zone, for the modulation of the record of sufficient optical change and improvement, preferred 1.5 or bigger refractive index n, for suppressing wavelength dependency and minimizing reconstruction error, preferred 3.0 or littler n.
In addition, for favourable recording sensitivity, preferred 0.02 or bigger extinction coefficient k, and preferred 0.3 or littler k, because can easily obtain 50% or bigger reflectivity.And refractive index n is improved by bigger absorption coefficient; Therefore preferred its log ε is 5 or bigger, and wherein ε is a molar absorption coefficient.
In addition, aspect light resistance, recording layer is preferably to 1,000,000 times or reproduce more frequently and have the stability of reproduction and light fastness, thereby can not fade after indoor placement.Can mix with other metal chelate dye by the bivalent metallic ion complex of the sour compound in general side and strengthen light resistance to satisfy above-mentioned requirements.
Substrate has the guide groove that the degree of depth is 1000 -2500 (guide groove) usually.The width of track pitch is generally 0.7 μ m-1.0 μ m, but for more jumbo application, the width of track pitch is preferably 0.7 μ m-0.8 μ m.The well width of representing with half-band width is preferably 0.18 μ m-0.4 μ m.Well width is preferably 0.18 μ m or bigger, because can obtain enough tracking error signal intensity.In addition, well width is preferably 0.40 μ m or littler, because can suppress the horizontal transmission of recording section in record.
Next the structure of optical recording media of the present invention is described.
Figure 1A-1D is the cross sectional representation that shows the example of the layer composition that is applicable to optical recording media of the present invention.These are examples of primary writing in multi-time reading out type CD.
As shown in Figure 1A, described layer is formed the structure with the recording layer 2 that forms in substrate of being included in 1.Shown in Figure 1B, described layer composition further is provided with recording layer 2 via bottom (undercoatlayer) 3 as required in substrate 1.Shown in Fig. 1 C, described layer composition further has protective layer 4 as required.Shown in Fig. 1 D, described layer composition further has hard conating 5 as required on the outer surface of substrate 1 in Fig. 1 C.
Fig. 2 A-2C is the cross sectional representation that shows layer example of forming of another structure that is applicable to optical recording media of the present invention.These are examples of CD-R medium.
As shown in Fig. 2 A-2C, layer composition has the structure that metallic reflector 6 is set on the recording layer 2 that is included in the composition of layer described in Figure 1A-1D.For example, Fig. 1 C is corresponding to Fig. 2 B, and Fig. 1 D is corresponding to Fig. 2 C, and Fig. 2 A is arranged on the structural structure that is provided with protective layer 4 among Figure 1A with metallic reflector 6.
Fig. 3 H-3J is the cross sectional representation that shows layer example of forming of the another structure that is applicable to optical recording media of the present invention.These are examples of dvd media.
As shown in Fig. 3 A-3C, layer composition has the structure that adhesive layer 8 and protectiveness substrate 7 are set on the protective layer 4 that is included in Fig. 2 A-2C middle level composition.For example, Fig. 2 A is corresponding to Fig. 3 A, and Fig. 2 B is corresponding to Fig. 3 B, and Fig. 2 C is corresponding to Fig. 3 C.
Further, when optical recording media of the present invention was used as the primary writing in multi-time reading out type dvd media, the basic structure of optical recording media had the structure of wherein using adhesive lamination first substrate and second substrate by recording layer.In this case, the recording layer sandwich construction that can form the single layer structure of organic dyestuff or form wherein lamination metallic reflector on as the organic dye layer of recording layer is to improve reflectivity.Layer form can make bottom or protective layer between recording layer and substrate or described structure can be with recording layer, substrate and bottom or protective layer lamination to improve performance.Modal structure comprises first substrate, organic dye layer, metallic reflector, protective layer, adhesive layer and second substrate according to following order.
Below illustrate in greater detail hard conating and protectiveness substrate on the substrate that forms optical recording media of the present invention, recording layer, bottom, metallic reflector, protective layer, adhesive layer, the substrate surface.
＜substrate 〉
When base side writes down and reproduce, for the performance requirement of substrate, substrate must be transparent with respect to the laser beam that is applied.When the recording layer side writes down and reproduce, and do not require that substrate is transparent.Therefore, in the present invention when two substrates accompany other layers, and do not require a substrate, for example first substrate is transparent, as long as i.e. second substrate of another substrate is transparent.
The example of base material comprises: plastics such as polyester, acrylic resin, polyamide, polycarbonate resin, vistanex, phenolic resins, epoxy resin and polyimides; Glass, pottery and metal.
Herein, on can surface when only using a substrate and when two substrates being used for the outermost surface of medium, can on the surface of first substrate, form the guide groove of tracking (tracking) usefulness and base tunnel (guide pit) and the further preformat (preformat) of address signal in substrate.
＜recording layer 〉
Recording layer is the information layer that can write down by the more caused optical change of the irradiation of laser beam wherein, and described recording layer must comprise two or more sour metal chelate compounds in side with identical ligands and different central metals used in the present invention at least.In other words, aspect the formation of recording layer, be used in combination the multiple sour metal chelate compound in side with identical ligands used in the present invention.
In addition, although the sour metal chelate compound of side used in the present invention can be used as dyestuff,, can construct recording layer by mixing or other organic dyestuff of lamination in order to improve optical characteristics, recording sensitivity and characteristics of signals.
The example of organic dyestuff comprises: azo dyes, first
The metal chelate compound of dyestuff and two pyrroles's methylene dyes; Methine dyes, phthalocyanine dye, croconium dyestuff, pyrans dyestuff, naphthoquinone dyestuff, anthraquinone (indanthrene) dyestuff, xanthene dye, kiton colors, azulenes dyestuff, tetrahydrochysene choline dyestuff, luxuriant and rich with fragrance dyestuff, triphen thiazine dye; And their metal chelate compound.These dyestuffs can use separately or two or more are used in combination.From further raising light resistance, special preferable alloy chelate compound.
In above-mentioned dyestuff, metal and metallic compound such as In, Te, Bi, Se, Sb, Ge, Sn, Al, Be, TeO
2, SnO, As and Cd can dispersion mixture or the form of the layer of lamination use.
In addition, dyestuff can by with polymeric material for example ionomer resin, polyamide, vinylite, natural polymer, silicone, liquid rubber and silane coupler disperse to mix and involved, perhaps can use stabilizing agent such as transition metal complex, dispersant, fire retardant, lubricant, antistatic additive, surfactant and plasticizer together in order to improve performance.
Recording layer can be made by usual way such as vapour deposition, sputter, CVD and solution coat.Using under the situation of rubbing method, the organic dyestuff of the sour metal chelate compound in the above-mentioned side of comprising is dissolved in the organic solvent and by normally used coating process such as spraying process, rolling method, dip coating and spin-coating method is being coated with.
The example of organic solvent comprises alcohols such as methyl alcohol, ethanol and isopropyl alcohol; Ketone such as acetone, methyl ethyl ketone and cyclohexanone; Acid amides such as N, dinethylformamide and N, N-dimethylacetylamide; Sulfoxide such as methyl-sulfoxide; Ethers such as oxolane, two alkane, diethyl ether and glycol monomethyl methyl ether; Ester class such as methyl acetate and ethyl acetate; Aliphatic halogenated hydrocarbons such as chloroform, carrene, dichloroethanes, carbon tetrachloride and trichloroethanes; Aromatic compound such as benzene, dimethylbenzene, monochloro-benzene and dichloro-benzenes; Cellosolve such as methyl cellosolve, ethoxy ethanol; Hydro carbons such as hexane, pentane, cyclohexane and hexahydrotoluene; With fluoridize alcohols as 2,2,3, the 3-tetrafluoropropanol.
The thickness of recording layer is preferably 100 -100,000 (10 μ m), more preferably and be suitably 200 -2,000 .
＜bottom 〉
Bottom can be used for following purpose: (a) improve adhesion, (b) anti-sealing or gas permeation (c) improve the storage stability of recording layer, (d) improve reflectivity, (e) at the bottom of the protecting group and recording layer avoid solvent and (f) form guide groove, base tunnel and preformat.
For purpose (a), can use the polymeric material of various polymeric materials, for example ionomer resin, polyamide, vinylite, natural resin, natural polymer, silicone, liquid rubber and silane coupler.In addition, for purpose (b) and (c), except above-mentioned polymeric material, can also use inorganic compound such as SiO
2, MgF
2, SiO, TiO
2, ZnO, TiN and SiN, and also have metal or semimetal such as Zn, Cu, Ni, Cr, Ge, Se, Au, Ag and Al.In addition,, can use metal such as Al and Ag for purpose (d), and organic film such as methine dyestuff and xanthene dye with metallic luster; For purpose (e) and (f), can use ultraviolet curable resin, thermosetting resin and thermoplastic resin.
Bottom preferably has 0.01 μ m-30 μ m, the more preferably thickness of 0.05 μ m-10 μ m.
＜metallic reflector 〉
As the material of metallic reflector, can use the anticorrosive elemental metals or the semimetal that can obtain high reflectance.Its instantiation comprises Au, Ag, Cr, Ni, Al, Fe, Sn and Cu.Wherein, with regard to reflectivity and productive rate, most preferably Au, Ag, Al and Cu, and these metals and semimetal can use separately or use as two or more alloy.
As the film build method of metallic reflector, can use the method for for example chemical deposition and sputter.Metallic reflector preferably has 50 -5000 , more preferably the thickness of 100 -3000 .
Protective layer on the＜substrate surface and hard conating 〉
Protective layer on the substrate surface or hard conating are used for following purpose: (a) protection recording layer (reflection-absorption layer) avoids scratch, dust and stain, (b) improves the storage stability of recording layer (reflection-absorption layer) and (c) improves reflectivity.
For these purposes, listed material can be used for bottom.In addition, material such as SiO and SiO
2Can be used as inorganic material.In addition, the example of organic material comprises heat-softened resin, heat fusing resin and ultraviolet curable resin such as PMA, Merlon, epoxy resin, polystyrene, mylar, vinylite, cellulose, aliphatic hydrocarbon resin, aromatic resins, natural rubber, styrene butadiene resin, neoprene, wax, alkyd resins, drying oil and rosin.Wherein, ultraviolet curable resin is the protective layer on the most preferred substrate surface or the example of hard conating because of its excellent productive rate.
Protective layer on the substrate surface or hard conating preferably have 0.01 μ m-30 μ m, the more preferably thickness of 0.05 μ m-10 μ m.
In the present invention, similar to the situation of recording layer, protective layer on the substrate surface and hard conating can comprise additive such as stabilizing agent, dispersant, fire retardant, lubricant, antistatic additive, surfactant and plasticizer.
＜protectiveness substrate 〉
When from protectiveness base side illuminating laser beam, described protectiveness substrate must be transparent to the laser beam that is applied, yet when it only was used as baffle, the transparency was just unimportant.
The material that can be used for the protectiveness substrate is just in time identical with the above-mentioned material that is used for substrate, and described material comprises plastics such as polyester, acrylic resin, polyamide, polycarbonate resin, vistanex, phenolic resins, epoxy resin and polyimides, glass, pottery and metal.
＜adhesive layer 〉
Described adhesive layer be with can be with two kinds of optical recording medias and protectiveness substrate bonding and can not damage that the material of optical recording media desired properties forms layer.Described material has no particular limits, but considers productive rate, and adhesive layer is preferably formed by the adhesive of ultraviolet curing or heat fusing.
Aspect optical recording media of the present invention, the change of the part that the part that is contained in the sour metal chelate compound of multiple side that its recording layer of standardization is comprised, that use as mixture perhaps can the sour metal chelate compound in the side of preventing.Therefore, the mixture solution of the sour metal chelate compound in side can keep the stability after its long-term storage stability and the repeated use, and the concentration determination of the sour metal chelate compound in side becomes possibility.When recording layer forms by the mixture that uses the sour metal chelate compound of this multiple side, might provide the optical recording media that has good light resistance and be applicable to primary writing in multi-time reading out type DVD disc system.
In addition, preferably in the recording layer of optical recording media of the present invention, comprise and have divalent metal as the sour metal chelate compound in the side of its central metal with have metal except divalent metal as the sour metal chelate compound in the side of its central metal, make it possible to accurately control optical characteristics like this, give the good optical characteristics of no record wavelength dependency, the photodegradation of caused recording layer is penetrated in the illumination that improves light resistance and prevent to be used for duplicate record and reproduction.Therefore, compare with for example using the conventional optical recording media of the sour compound in the side of comprising and its aluminium chelate compound, optical recording media of the present invention is given with good light resistance and optical characteristics.
Therefore, optical recording media of the present invention can be applicable to, for example, the DVD disc system comprises jumbo primary writing in multi-time reading out type optical data disk such as jumbo primary writing in multi-time reading out type compact disk, DVD-R and DVD+R and big capacity light-card (optical card).Certainly, optical recording media of the present invention can be used for the CD-R medium.
In addition, add and mix other metal chelate dye such as azo dyes, first as required
Dyestuff and two pyrroles's methylene dyes can further improve light resistance.In addition, with respect to record and the refractive index of playback light and by to reflecting layer use special metal or its alloy, might provide the optical recording media that can write down and reproduce with stable high reflectance and high amplitude modulation by control recording layer (individual layer).
In addition, even optic recording method and optical recorder that the use of optical recording media of the present invention has realized there is not the recording wavelength dependence under the 600nm-720nm recording wavelength and also can implement stable record and reproduction with the light reirradiation.
The present invention will be described in more detail hereinafter with reference to embodiment, but these embodiment and be not interpreted as limitation of the present invention.In addition, the used sour metal chelate compound in side can be according to the method manufacturing described in the open No.WO2002/50190 in the world in following examples and the comparative example.
(embodiment 1)
By the sour compound in the side that will have structural formula A-11 in the table 2 as the aluminium chelate compound (A-11-Al) of part with have identical A-11 as the nickel chelate compound (A-11-Ni) of part with 50 parts of A-11-Al: the mass ratio of 50 parts of A-11-Ni mixes and this mixture is dissolved in 2,2,3, the 3-tetrafluoropropanol prepares homogeneous solution (0.8 quality %).
Then this solution is coated on the injection molding polycarbonate substrate that thickness is 0.6mm with circulator, it is 1 that this substrate has groove depth, 600 , half-band width are that 0.25 μ m and track pitch are the guide groove of 0.74 μ m, and formation thickness is the recording layer of the organic dye layer of 1,000 .Then the argentum reflecting layer that thickness is 1,200 is set by sputtering method, and by using the acrylic compounds photopolymer that the protective layer that thickness is 5 μ m is set on the reflecting layer.In addition, with the injection molding polycarbonate substrate of acrylic compounds photopolymer lamination 0.6mm, and the preparation optical recording media.
Rest solution was at room temperature left standstill 14 days, and prepare optical recording media with identical method.Prepared optical recording media is assessed under the following conditions.
That is to say, be that 658nm, beam diameter are that semiconductor laser beam linear velocity with 3.5m/sec on each optical recording media of 1.0 μ m is carried out the tracking record with emission wavelength.Then, be that 658nm, reproducing power are that the continuous light of the semiconductor laser of 0.7mW reproduces with emission wavelength.Observe and reproduce waveform and measure the PI error.In addition, carry out light resistance test and storage test under the following conditions.Assessment result is shown in Table 4.
＜test condition 〉
The light resistance test: Xe light prolonged exposure is 50 hours under 40,000 illumination of reining in;
Store test: under 50 ℃ of temperature and 80% relative humidity, placed 800 hours;
In addition, with 10 times of solution dilutions after the part preparation just and as the phase chromatography-use sample solution.
Using the sample solution that is obtained to implement liquid chromatogram under the following conditions measures.Measurement result is shown among Fig. 4.In addition, this sample solution was at room temperature placed 14 days, and implemented liquid chromatogram with identical method and measure.The results are shown among Fig. 5.
＜liquid phase chromatogram condition 〉
Post: (4.6mm * 250mm), GLScience company makes Inertsil ODS-2
Column temperature: 35 ℃
The elutriant of elution solution: acetonitrile: ethyl acetate: water=55: 25: 20 (volume %)
Flow velocity: 0.5mL/min
Detection: 254nm
Injected sample volume: 5 μ L
Even Fig. 5 demonstrates in the solution that leaves standstill 14 days rear acid metal chelate compounds and also do not observe new peak, this has confirmed not form isomers or other compound and part and has not changed.
(comparative example 1)
By the sour compound in the side that will have the structural formula A-10 in the table 2 as the aluminium chelate compound (A-10-Al) of part with have table 3 in the sour compound in side of structural formula A-15 as the aluminium chelate compound (A-15-Al) of part with 80 parts of A-10-Al: the mass ratio of 20 parts of A-15-Al mixes mutually and this mixture is dissolved in 2,2,3, the 3-tetrafluoropropanol prepares homogeneous solution (0.1 quality %).With with embodiment 1 in identical method with this formulations prepared from solutions optical recording media and assess.Assessment result is shown in Table 4.In addition, with 10 times of solution dilutions after the part preparation just and as the phase chromatography-use sample solution.
With embodiment 1 in use the sample solution that is obtained to implement liquid chromatogram under the identical condition to measure.Measurement result is shown among Fig. 6.In addition, this sample solution was at room temperature placed 14 days, and implemented liquid chromatogram with identical method and measure.The results are shown among Fig. 7.
Fig. 7 demonstration has detected new peak, and this confirmation has formed new compound by two kinds of dissimilar aluminium chelate compounds.
(embodiment 2)
Compound with employed aluminium chelate compound (A-11-Al) among the embodiment 1 and nickel chelate compound (A-11-Ni) and following general formula (VIII) representative, hereinafter also can be described as compound (VIII), with mass ratio (A-11-Al): (A-11-Ni): (compound (VIII)) mutually mixes at 30: 30: 40.Then, by this mixture is dissolved in 2,2,3, the 3-tetrafluoropropanol prepares solution, makes that solid concentration is 1 quality %.Then this solution is coated on the injection molding polycarbonate substrate that thickness is 0.6mm with circulator, it is 1 that this substrate has groove depth, 600 , half-band width are that 0.25 μ m and track pitch are the guide groove of 0.74 μ m, and formation thickness is the recording layer of the organic dye layer of 1,000 .Then, by sputtering method argentum reflecting layer that thickness is 1,200 is set and by using the acrylic compounds photopolymer that the protective layer that thickness is 5 μ m is set on the reflecting layer.In addition, with the injection molding polycarbonate substrate of acrylic compounds photopolymer lamination 0.6mm, and the preparation optical recording media.
Under the following conditions prepared optical recording media is assessed.
With emission wavelength is that 658nm, beam diameter are that the semiconductor laser beam of 1.0 μ m is carrying out the tracking record under with the linear velocity of 3.5m/sec on the optical recording media.Then, be that 658nm, reproducing power are that the continuous light of the semiconductor laser of 0.7mW reproduces with emission wavelength.Observe the reproduction waveform and measured the PI error.In addition, carry out light resistance test and storage test under the following conditions.Assessment result is shown in Table 4.
＜test condition 〉
The light resistance test: Xe light prolonged exposure is 50 hours under 40,000 illumination of reining in;
Storage test: under 50 ℃ of temperature and 80% relative humidity, placed 800 hours;
(embodiment 3)
Dyestuff in the spin coater that has been scattered in the spin-coating method with embodiment 2 reclaims and is dissolved in 2,2,3, in the 3-tetrafluoropropanol.With 10 times of this solution dilutions and as above-mentioned identical condition under use liquid chromatography for measuring concentration.The concentration of A-11-Al, A-11-Ni and compound (VIII) is respectively 0.308%, 0.332% and 0.389% as calculated.Replenish not enough amount and prepare dye solution once more so that solid concentration is 1.0% and ratio of components (A-11-Al) according to these results: (A-11-Ni): (compound (VIII)) is 30: 30: 40.Use this formulations prepared from solutions optical recording media with the method identical with embodiment 2.Method test light resistance and the storage property identical to prepared used by optical recording medium and embodiment 2.The result is shown in the following table 4 similarly.
(embodiment 4)
To prepare recording medium with embodiment 2 identical methods, difference is with having structural formula A-6 in the table 1 as the aluminium chelate compound (A-6-Al) of part with have A-6 equally as the sour metal chelate compound of employed side among copper chelate compound (A-6-Cu) the replacement embodiment 2 of part, compound with following general formula (IX) representative, hereinafter be also referred to as compound (IX), replace compound (VIII), the mixing quality ratio of above-claimed cpd changes 40: 20: 40 into.Method test light resistance and the storage property identical to prepared used by optical recording medium and embodiment 2.The result is shown in the following table 4 similarly.
Wherein, in general formula (IV), Ph represents phenyl.
(embodiment 5)
Dyestuff in the spin coater that has been scattered in the spin-coating method with embodiment 4 reclaims and is dissolved in 2,2,3, in the 3-tetrafluoropropanol.With 10 times of this solution dilutions and as above-mentioned identical condition under use liquid chromatography for measuring concentration.The concentration of A-6-Al, A-6-Cu and compound (IX) is 0.411%, 0.212% and 0.385% as calculated.Replenish not enough amount and prepare dye solution once more according to these results: (A-6-Cu): (IX) be 40: 20: 40 so that solid concentration is 1.0% and ratio of components (A-6-Al).With the method identical with embodiment 4 with this formulations prepared from solutions optical recording media.Method test light resistance and the storage property identical to prepared used by optical recording medium and embodiment 4.The result is shown in the following table 4 similarly.
Table 4
| Embodiment | Initial value | After the light resistance test | After the storage test | ||||
| Reflectivity (%) | The PI error | Reflectivity (%) | The PI error | Reflectivity (%) | The | ||
| Embodiment | |||||||
| 1 | Just after the preparation | 62 | 8 | 50 | 38 | 47 | 50 |
| After 14 days | 61 | 9 | 50 | 42 | 48 | 53 | |
| Comparative example 1 | After the preparation | 68 | 11 | 44 | 150 | 44 | 250 |
| After 14 days | 60 | 35 | 38 | 288 | 37 | 355 | |
| |
54 | 3 | 54 | 13 | 53 | 23 | |
| |
54 | 4 | 53 | 18 | 53 | 22 | |
| Embodiment 4 | 48 | 6 | 49 | 17 | 48 | 23 | |
| |
49 | 6 | 48 | 20 | 47 | 30 | |
The result of table 4 shows, as the use of the total part of the sour metal chelate compound of multiple side in the optical recording media of the present invention, even even make can not cause after being retained in the organic solvent because of the confusion of part in the chelate yet change and behind light resistance test and storage property testing the variation of PI sum of errors reflectivity also less.In addition, this result also shows, by the dyestuff (solution of the sour metal chelate compound in side) that is scattered after the spin coating is utilized and use its concentration of liquid chromatography for measuring again after with its recovery, might obtain and reclaim preceding identical performance.
The sour metal chelate compound in side shown in the description list 3 in preparation embodiment 1-3 below is as the preparation embodiment of A-8-Ni, A-8-Cu and A-8-Zn.Other table among the 1-3 the listed sour metal chelate compound in side can to prepare embodiment according to these synthetic similarly.
(preparation embodiment 1)
The preparation of＜A-8-Ni 〉
In the mixture of the compound of the following general formula of 1.50g (X) representative and 0.36g four water nickel acetates, add 10.5mL ethyl acetate, 4.5mL methyl alcohol and 0.01g acetate.Under 60 ℃ of temperature, make this mixture reaction 3 hours then.The precipitation of filtering reaction and acquisition 1.45g side acid metal chelate compound (compd A-8-Ni).The mass spectrum result of compd A-8-Ni is MS (M-) m/z:1166, has confirmed that the compound that is obtained is a target compound.
(preparation embodiment 2)
The preparation of＜A-8-Cu 〉
In the mixture of the compound of the above-mentioned general formula of 1.50g (X) representative and 0.27g copper sulfate monohydrate, add 7.5mL ethyl acetate, 7.5mL methyl alcohol and 0.01g acetate.Under 60 ℃ of temperature, make this mixture reaction 5 hours then.The precipitation of filtering reaction and acquisition 1.39g side acid metal chelate compound (compd A-8-Cu).The mass spectrum result of compd A-8-Cu is MS (M-) m/z:1173, has confirmed that the compound that is obtained is a target compound.
(preparation embodiment 3)
The preparation of＜A-8-Zn 〉
In the mixture of the compound of the above-mentioned general formula of 1.00g (X) representative and 0.19g acetopyruvic acid zinc, add 12.0mL ethyl acetate and 0.05g acetate.Under 60 ℃ of temperature, make this mixture reaction 2 hours then.The precipitation of filtering reaction and acquisition 0.95g side acid metal chelate compound (compd A-8-Zn).The mass spectrum result of compd A-8-Zn is MS (M-) m/z:1172, has confirmed that the compound that is obtained is a target compound.
(embodiment 6)
With the acid of the A-16-Al side in the A-11-Ni in the table 2 and the table 3 metal chelate compound with the compound of following general formula (XI) representative, hereinafter also can be described as compound (XI) with (A-11-Ni): (A-16-Al): be that 30: 30: 40 mass ratio mixes mutually (XI).Then, by this mixture is dissolved in 2,2,3, prepare solution in the 3-tetrafluoropropanol so that solid concentration is 1 quality %.With the method identical with embodiment 2 with this formulations prepared from solutions optical recording media and assess.The results are shown in the table 5.Then this solution is coated on the injection molding polycarbonate substrate that thickness is 0.6mm with circulator, it is 1 that this substrate has groove depth, 600 , half-band width are that 0.25 μ m and track pitch are the guide groove of 0.74 μ m, and formation thickness is the recording layer of the organic dye layer of 1,000 .
Wherein, in general formula (XI), Ph represents phenyl.
Prepared optical recording layer is assessed under the following conditions.
With emission wavelength is that 658nm, beam diameter are that semiconductor laser beam linear velocity with 3.5m/sec on optical recording media of 1.0 μ m is carried out the tracking record.Then, be that 658nm, reproducing power are that the continuous light of the semiconductor laser of 0.7mW reproduces with emission wavelength.Observe the reproduction waveform and measured the PI error.In addition, light resistance test and storage test have been carried out under the following conditions.Assessment result is shown in Table 5.
＜test condition 〉
The light resistance test: Xe light prolonged exposure is 50 hours under 40,000 illumination of reining in;
Storage test: under 50 ℃ of temperature and 80% relative humidity, placed 800 hours;
(embodiment 7)
To prepare optical recording media with embodiment 6 identical methods, difference is with two kinds, promptly A-2-Zn in the table 1 and the A-16-Al in the table 3 replace the sour metal chelate compound of employed side among the embodiment 2, the compound that replaces general formula (XI) representative with the compound of following general formula (XII) representative, (A-2-Zn): (A-16-Al): mixing quality ratio (XII) becomes 40: 40: 20, silver in the reflecting layer replaces with gold, and the thickness in reflecting layer becomes 1,300 .Prepared used by optical recording medium and embodiment 6 identical methods are tested.The result is shown in the following table 5 similarly.
Wherein, in general formula (XII), Ph represents phenyl.
(embodiment 8)
To prepare optical recording media with embodiment 7 identical methods, difference is with two kinds, promptly A-10-Cu in the table 2 and the A-8-Al in the table 2 replace the sour metal-chelating of employed side chemical combination among the embodiment 7, replace the compound of general formula (XII) representative with the compound of general formula (XIII) representative, and (A-10-Cu): (A-8-Al): mixing quality ratio (XIII) becomes 20: 40: 40.
Prepared used by optical recording medium and embodiment 6 identical methods are tested, and the result is shown in the following table 5 similarly.
(embodiment 9)
To prepare optical recording media with embodiment 8 identical methods, difference is with two kinds, promptly A-8-Ni in the table 2 and the A-16-Al in the table 3 replace the sour metal chelate compound of employed side among the embodiment 8, and (A-8-Ni): (A-16-Al): mixing quality ratio (XIII) becomes 15: 50: 25.
Method test light resistance and the storage property identical to prepared used by optical recording medium and embodiment 6.The result is shown in the following table 5 similarly.
(comparative example 2)
Preparing optical recording media with embodiment 6 identical methods, the mixture that difference only is to replace A-11-Ni and A-16-Al among the embodiment 6 with A-11-Ni is as the sour metal chelate compound in side and with (A-11-Ni): mixing quality ratio (XI) becomes 60: 40.
Prepared used by optical recording medium and embodiment 6 identical methods are tested.The result is shown in the following table 5 similarly.
(comparative example 3)
Preparing optical recording media with embodiment 7 identical methods, difference only is to replace A-2-Zn and A-16-Al as the sour metal chelate compound in side and with (A-2-Zn) with A-2-Zn: mixing quality ratio (XII) becomes 80: 20.Prepared used by optical recording medium and embodiment 6 identical methods are tested.The result is shown in the following table 5 similarly.
(comparative example 4)
Prepare optical recording media with the method identical with embodiment 8, difference only is to replace among the embodiment 8 A-10-Cu and A-8-Al as the sour metal chelate compound in side and with (A-10-Cu) with A-10-Cu: mixing quality ratio (XIII) becomes 60: 40.
Prepared used by optical recording medium and embodiment 6 identical methods are tested.The result is shown in the following table 5 similarly.
(comparative example 5)
Prepare optical recording media with the method identical with embodiment 7, difference only is A-16-Al as the sour metal chelate compound in side and do not use A-2-Zn.
Prepared used by optical recording medium and embodiment 6 identical methods are tested.The result is shown in the following table 5 similarly.
(comparative example 6)
Prepare optical recording media with the method identical with embodiment 7, difference be will preparation embodiment 1 in the sour compound in side of general formula (X) of nonmetal complex compound be used to replace the sour metal chelate compound in side of embodiment 7.
Prepared used by optical recording medium and embodiment 6 identical methods are tested.The result is shown in the following table 5 similarly.
Table 5
| Embodiment | Initial value | After the light resistance test | After the storage test | |||
| Reflectivity (%) | The PI error | Reflectivity (%) | The PI error | Reflectivity (%) | The | |
| Embodiment | ||||||
| 6 | 49 | 1 | 48 | 10 | 47 | 18 |
| Embodiment 7 | 54 | 3 | 52 | 20 | 51 | 25 |
| Embodiment 8 | 48 | 5 | 49 | 13 | 48 | 20 |
| Embodiment 9 | 49 | 4 | 49 | 17 | 50 | 27 |
| Comparative example 2 | 38 | 25 | 37 | 33 | 38 | 44 |
| Comparative example 3 | 43 | 15 | 41 | 35 | 41 | 46 |
| Comparative example 4 | 33 | 35 | 34 | 43 | 33 | 51 |
| Comparative example 5 | 54 | 3 | 46 | 98 | 46 | 114 |
| Comparative example 6 | 58 | 2 | 45 | 153 | 45 | 164 |
Result in the table 5 shows, only comprising the sour metal chelate compound of a kind of side (comparative example 2-5) with recording layer wherein compares with the situation that recording layer only comprises the sour compound in side (comparative example 6) of nonmetal complex compound, have divalent metal in the recording layer (embodiment 6-9) as the sour metal chelate compound in the side of its central metal with have that metal except that divalent metal has reduced as the use of the sour metal chelate compound in the side of its central metal even light resistance test and the storage PI sum of errors reflectance varies after testing, and improved light resistance and kept optical characteristics simultaneously.
Industrial applicibility
Optical recording media of the present invention is specially adapted to primary writing in multi-time reading out type DVD disc system, because compare with the conventional optical recording media of the sour compound in the side of having and its aluminium chelate compound, it can improve light resistance and accurately control optical characteristics.
Claims (16)
1. optical recording media comprises:
Substrate and
The recording layer of the sour metal chelate compound in the suprabasil side of comprising,
Wherein said recording layer comprises the mixture of being made up of the sour metal chelate compound in the side with two or more different metals.
2. optical recording media according to claim 1, wherein said recording layer comprise having divalent metal as the sour metal chelate compound in the side of its metal with have metal except that divalent metal as the sour metal chelate compound in the side of its metal.
3. according to each described optical recording media among the claim 1-2, the sour metal chelate compound of wherein said side comprises identical part.
4. according to each described optical recording media among the claim 1-3, the sour metal chelate compound of wherein said side is by following general formula (I) representative:
Wherein, in general formula (I), R
1And R
2Identical or different, and represent hydrogen atom, can have substituent aliphatic group, can have substituent aralkyl, can have substituent aryl and maybe can have substituent heterocyclic radical;
The M representative has the metallic atom of coordination;
M represents integer 2 or 3; And
The X representative can have substituent aryl, can have substituent heterocyclic radical or [Z
1=CH-],
Z wherein
1Representative can have substituent heterocyclic radical.
5. optical recording media according to claim 4, the X in its formula of (I) are by following general formula (II) representative:
Wherein, in general formula (II), R
3And R
4Identical or different, and representative can have substituent aliphatic group or form with adjacent carbon atom and can have substituent alicyclic ring and maybe can have substituent heterocycle;
R
5Represent hydrogen atom, can have substituent aliphatic group, can have substituent aralkyl, maybe can have substituent aryl;
R
6To R
9Can be identical or different, and represent hydrogen atom, halogen atom, can have substituent aliphatic group, can have substituent aralkyl, can have substituent aryl, nitro, cyano group and maybe can have substituent alkoxyl; With
R
6To R
9In two functional groups adjacent each other can combine with two adjacent separately carbon atoms to form and can have substituent ring.
6. according to each described optical recording media among the claim 1-5, wherein said central metal is the metal that is selected from aluminium, nickel, copper and the zinc.
7. according to each described optical recording media among the claim 2-6, wherein said divalent metal is any at least metal that is selected from nickel, copper and the zinc.
8.. according to each described optical recording media among the claim 2-7, the wherein said metal that has except that divalent metal is the trivalent aluminium chelate compound as the sour anchor metal chelate compound in the side of its central metal.
9.. according to each described optical recording media among the claim 1-8, wherein said recording layer further comprises and is selected from azo-metal chelate dye, first
At least a metal chelate dye in metal chelate dye and the two pyrroles's methylene metal chelate dyes.
10.. optical recording media according to claim 9, the central metal of wherein said metal chelate dye are at least a metals that is selected from nickel, copper, cobalt, manganese and the oxidation alum.
11.. according to each described optical recording media among the claim 1-10, wherein for light with record and playback wavelength ± 5nm wavelength, the refractive index n of described recording layer as individual layer is 1.5≤n≤3.0, and extinction coefficient k is 0.02≤k≤0.3.
12. according to each described optical recording media among the claim 1-11, wherein said recording medium comprises the reflecting layer; And described reflecting layer is any in the alloy of gold, silver, copper, aluminium and these metals.
13. according to each described optical recording media among the claim 1-12, wherein said optical recording media is 0.7 μ m-0.8 μ m in suprabasil track pitch, well width is 0.18 μ m-0.40 μ m.
14., wherein can under the 600nm-720nm recording wavelength, carry out record according to each described optical recording media among the claim 1-13.
15. an optic recording method is included in the step that writes down in each described optical recording media under the 600nm-720nm wavelength in according to claim 1-14.
16. an optical recorder that wherein contains recording medium, wherein said optical recorder is by writing down to described recording medium irradiates light and reproducing; And described recording medium is according to each described optical recording media among the claim 1-14.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP088692/2005 | 2005-03-25 | ||
| JP2005088692A JP2006264241A (en) | 2005-03-25 | 2005-03-25 | Optical recording medium, optical recording method using the same and optical recording device |
| JP088693/2005 | 2005-03-25 |
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|---|---|
| CN101166632A true CN101166632A (en) | 2008-04-23 |
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| CN (1) | CN101166632A (en) |
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| CN103824571A (en) * | 2012-11-15 | 2014-05-28 | 索尼公司 | Optical recording medium substrate and method of manufacturing the same, and optical recording medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5037155B2 (en) | 2006-02-21 | 2012-09-26 | 株式会社リコー | Optical information recording medium and manufacturing method thereof |
| WO2011026054A2 (en) * | 2009-08-31 | 2011-03-03 | Millenniata, Inc. | Reliability testing of optical media using simultaneous heat, humidity, and light |
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| JP4183919B2 (en) * | 2000-03-07 | 2008-11-19 | 株式会社リコー | Optical recording medium and optical recording method using the same |
| JP2005044491A (en) * | 2003-07-10 | 2005-02-17 | Ricoh Co Ltd | Optical recording medium and its manufacturing method |
-
2005
- 2005-03-25 JP JP2005088692A patent/JP2006264241A/en active Pending
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| CN103824571A (en) * | 2012-11-15 | 2014-05-28 | 索尼公司 | Optical recording medium substrate and method of manufacturing the same, and optical recording medium |
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