CN100334158C - High-solubility metal-complex azo dye for DVD-R optical disk - Google Patents
High-solubility metal-complex azo dye for DVD-R optical disk Download PDFInfo
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- CN100334158C CN100334158C CNB031169430A CN03116943A CN100334158C CN 100334158 C CN100334158 C CN 100334158C CN B031169430 A CNB031169430 A CN B031169430A CN 03116943 A CN03116943 A CN 03116943A CN 100334158 C CN100334158 C CN 100334158C
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Abstract
The present invention discloses high-solubility metal complex azo dyes for DVD-R optical disks. The dyes comprise tert-butyl substituted groups, have good solubility and high thermal stability in organic solvents, and ultraviolet visible absorption wavelength can meet the requirements of DVD-R optical disks, and thus, the high-solubility metal complex azo dyes have wide application prospect in the DVD-R optical disks.
Description
Technical field
The present invention relates to the preparation of a class DVD-R CD with the high-dissolvability metal complex azo dye.
Background technology
Optical recording is a high-new information storage technology from development at the beginning of the seventies.In the information-recording material field, the disc recording medium with adopting laser to write down and read is referred to as CD.Since first read-only MD mini disk CD (compact disk) that nineteen eighty-two SONY and PHILIPS company release, CD with regard to since have recording density height, capacity greatly, random access, the preservation life-span is long, reliable and stable and series of advantages such as easy to use and at sound, look the field and computer realm is widely used.Before DVD occurs, although also occurred read-only, once write, writing optical disk storage media repeatedly, the recording capacity of these CDs is limited, can not satisfy growing new demand, thereby needs more jumbo CD to occur.DVD develops under such background, and its main characteristics is exactly that capacity is big.But no matter be CD or DVD, they all are to utilize the method for press mold to produce, and data just are recorded in the inside after producing, and can not write data inwards again.In order to satisfy this needs that can write data, cd-recordable has just appearred.
Cd-recordable is made up of basal disc, recording layer, reflecting layer and protective layer.Basal disc is made by transparent resins such as polycarbonate, polymethyl acrylates; recording layer is to be made by the mode of spin-coating by dyestuff; the reflecting layer is metal by gold and silver, aluminium etc.; protective layer then is to use the method for rotary coating at reflecting layer last layer uv-hardening resin; under the uviolizing of high voltage mercury lamp, harden then, form protective layer.The record of data is that the laser radiation recording layer with certain wavelength makes it that irreversible physics or chemical transformation take place, thereby change reflection of light and intensity in transmission is come recorded information.Find out that from above-mentioned the key component of cd-recordable is a recording layer, just optical recording medium.The key that improves capacity of optical storage and performance is to develop new optical recording medium.Because the DVD-R CD is different with the wavelength of the semiconductor laser of reading with the CD-R video disc recording, the optical recording medium that is used for the CD-R CD can not be used for the DVD-R CD, so the prerequisite of development DVD-R CD is the new optical recording medium of exploitation.This new optical recording medium requires at the 630nm-650nm place suitable absorption and reflection are arranged, and good solubleness is arranged in organic solvent, and enough thermostabilitys are arranged, and decomposition temperature is higher than 250 ℃.In addition also to be easy to preparation, low price.
In recent years, the more optical recording medium that is used for the DVD-R CD of research mainly contains cyanine dyes, phthalocyanine pigment and metal complex azo dye.Cyanine dyes is the dyestuff that a class contains methine chain.Cyanine dyes has high specific absorption and reflectivity, thereby obtains higher signal to noise ratio, the method coating of taking spin coating that its solubleness high energy in the coating solvent is more convenient.But the light stability of cyanine dyes is poor, and the persistence of sense data is poor.Phthalocyanine pigment is one of organic medium that is used in early days optical disk system.Phthalocyanine pigment has the structure of organometallic complex and high conjugated structure, and from chemical stability with to optical absorption intensity, the metal phthalocyanine dyestuff is a very good light absorber.But its luminance factor cyanine dyes is low, and the character of general read/write is not as cyanine dyes, and under the effect of light, heat or solvent, crystalline structure very easily changes, and this do great harm in optical disk system.And its poorly soluble in organic solvent, cost an arm and a leg, metal complex azo dye is the weaving organic dye of a class widespread use, and along with the development of photoelectron technology, it has caused people's very big interest as nonlinear optical material and optical recording medium in recent years.Metal complex azo dye is as optical recording medium, good light stability, and absorbing wavelength can be adjusted Heat stability is good by the substituting group of adjusting on it.Owing to have above advantage, so metal complex azo dye is used in the optical recording medium as the DVD-R CD especially.Patent EP0887202; US 6284877; US 6214519; EP 0,981 132; US 20020015915 and document Mol.Cryst.Liq.Cryst.2001,371:305-308, Bull.Chem.Soc.Jpn.2002,75:2067-2070 etc. have reported some metal complex azo dyes as optical recording medium, but they are not all made reports to the solubleness of these dyestuffs.From our test case to the solubleness of the dyestuff of bibliographical information, the result is unsatisfactory.
Summary of the invention
The objective of the invention is to, disclose a class and be soluble in organic solvent, be used for the novel metal complexing azoic dyestuff of DVD-R CD optical recording medium.
Technical conceive of the present invention is such:
The present invention is with 2, and 4-DI-tert-butylphenol compounds and p-tert-butylphenol are the synthetic azoic dyestuff of the diazonium salt generation coupled reaction of coupling component and aromatic amine or heterocyclic amine, obtain metal complex azo dye with complexing of metal ion then.Owing in dyestuff, introduced tertiary butyl substituting group, so their solubleness in organic solvent improves greatly.Owing to be metal complex, their thermostability is all higher.Their absorption curve can be adjusted so that it is applicable to the DVD-R CD by the structure of adjusting aromatic amine.And the preparation method is simple for this class dyestuff, low price.
Realize the technical scheme of the object of the invention:
The said metal complex azo dye of the present invention is the compound with following general structure:
In the formula: A is for being substituted with the group (as hydroxyl, sulfydryl, amino, carboxyl, sulfonic group or sulfoamido) that contains reactive hydrogen or aromatic nucleus (as phenyl ring or naphthalene nucleus) or its substitutive derivative of methoxyl group at the azo-group ortho position; Or comprise heterocycle or its substitutive derivative of an energy and the nitrogen-atoms of complexing of metal ion at least; R is hydrogen or C
1-C
4Alkyl; M is a nickel, chromium, cobalt, copper, iron, manganese or zinc; M=1 or 2.
Above-mentioned nitrogen heterocyclic ring comprises pyridine, thiazole, thiadiazoles, benzothiazole, quinoline or imidazoles; The substituting group of aromatic nucleus or heterocyclic substitutive derivative is a nitro, halogen atom, carboxyl, sulfonic group, C
1-C
4Alkyl, sulfonamido and/or aromatic base.
The synthetic method of compound of the present invention comprises the steps:
(1) a: aromatic amine is got aromatic diazo salt after the usefulness Sodium Nitrite diazotization in solvent 1.B: heterocyclic amine is got the heterocycle diazonium salt after the usefulness nitrosyl sulfuric acid diazotization in solvent 2.(2) will in solvent 3 coupled reaction take place with coupling component respectively by step (1) gained two class diazonium salts, collect azoic dyestuff from reaction product.(3) a: will in solvent 4, react by aromatic amine azoic dyestuff that makes in the step (2) and metal ion 1, and collect metal complex azo dye.B: will in solvent 5, react by heterocyclic amine azoic dyestuff that makes in the step (2) and metal ion 2, and collect metal complex azo dye.
Wherein: said aromatic amine is that amino ortho position has phenyl ring or the naphthalene nucleus that contains active hydrogen group or methoxyl group, and the said group that contains reactive hydrogen is a hydroxyl, sulfydryl, amino, carboxyl, sulfonic group or sulfoamido.Preferred aromatic amine is the substituted aniline that there is methoxyl group at the ortho position.
Said heterocyclic amine is the pyridine that there is nitrogen-atoms at amino ortho position, thiazole, thiadiazoles, benzothiazole, quinoline, imidazoles.Nitrogen-atoms wherein can with complexing of metal ion.Preferably nitrogen heterocyclic ring amine is thiazole, thiadiazoles, benzothiazole, quinoline.More preferably nitrogen heterocyclic ring amine is 2-amino-1,3,4 thiadiazoles.
On said aromatic amine or the nitrogen heterocyclic ring amine substituting group can be arranged, comprise nitro, halogen atom, carboxyl, sulfonic group, sulfonamido, aromatic base and/or C
1-C
4Alkyl.
Said coupling component is the compound with following general structure:
In the formula: R is hydrogen or C
1-C
4Alkyl.
Said metal ion is a nickel, chromium, cobalt, copper, iron, manganese, zinc.Preferred metal ion 1 is a nickel, and preferred metal ion 2 is a chromium.
Solvent 1 among said step (1) a is a water, and temperature of reaction is-5 ℃-0 ℃, and the reaction times is 1 hour.
Solvent 2 among said step (1) b is an acetic acid: propionic acid (V/V)=2: 1, temperature of reaction are-5 ℃-0 ℃, and the reaction times is 3 hours.
Solvent 3 in the said step (2) is an ethanol, and temperature of reaction is-5 ℃-0 ℃, and the reaction times is 3 hours.
Solvent 4 among said step (3) a is an ethanol, and temperature of reaction is a room temperature, and the reaction times is 6 hours.
Solvent 5 among said step (3) b is DMF, and temperature of reaction is 150 ℃, and the reaction times is 6 hours.
Said nitrogen heterocyclic ring amine is with reference to J.Am.Chem.Soc.1946,68:871; J.Indian.Chem.Soc.1978, LV:401-404; JP 41-20944 (1966) institute reported method is synthesized, and all the other compounds are the commercially available prod.
Its solubleness in 4-methyl-organic solvents such as 4-hydroxyl-2 pentanone of the said metal complex azo dye of the present invention is good, the thermostability height, its decomposition temperature is all more than 250 ℃, and absorbing wavelength is suitable, at 630nm-650nm suitable absorption is arranged all at the ultraviolet-visible absorption curve, therefore be specially adapted to do DVD-R CD optical recording medium.
Description of drawings
Fig. 1 is the solid film absorption curve of dyestuff DYE-1.
Fig. 2 is the solid film absorption curve of dyestuff DYE-7.
Specific implementation method
Below in conjunction with concrete synthetic method and the solubleness in 4-methyl-4-hydroxyl-2 pentanone, the uv-absorbing in the pure solid film and the mensuration of decomposition temperature of setting forth above-mentioned dyestuff of example.But the cited case does not limit protection scope of the present invention.
Embodiment 1
Dyestuff DYE-1's is synthetic:
Synthesizing of azoic dyestuff:
The 1.4g8-quinolylamine is dissolved in the solution of being made up of 10ml propionic acid and 20ml acetic acid, is cooled to-5 ℃-0 ℃.Under stirring state, 3.55g43% nitrosyl sulfuric acid solution is slowly joined in this solution.Adding the back continues to stir 3 hours.In whole process, keep temperature-5 ℃-0 ℃.
With 2.1g2, the 4-DI-tert-butylphenol compounds is dissolved in the 30ml ethanol, regulates pH=10-12 with dilute sodium hydroxide, is cooled to-5 ℃-0 ℃.Under agitation slowly diazonium liquid is added wherein, this process approximately needs 30 minutes.Adding the back continues to stir 3 hours.Whole process remains pH=10-12, temperature-5 ℃-0 ℃.Reaction finishes the back and regulates pH=6-7 with dilute hydrochloric acid, separates out a large amount of red solid.Solid collected by filtration, oven drying at low temperature.Get the orange red solid of 3g with ethyl alcohol recrystallization, m.p.191 ℃-193 ℃, yield 85%.
1H-NMR(CDCl
3)(ppm)：1.39(s，9H)，1.52(s，9H)，7.45(s，1H)，7.54(m，1H)，7.68(t，1H)，7.74(s，1H)，7.91(d，1H)，8.20(d，1H)，8.25(d，1H)，9.15(d，1H)。
Synthesizing of metal complex azo dye:
Azoic dyestuff 1.8g is dissolved in the 100ml ethanol, and 0.62g four hydration nickel acetates are dissolved in the 50ml ethanol, join in the dye solution.Stirring at room 6 hours with the solvent pressure reducing and steaming, is separated out black solid.Collect solid, use ethyl acetate: sherwood oil=column chromatography got the 1.6g black solid in 1: 2, yield 88%.ESI：729.6(M
+)。
The pure solid film uv-visible absorption spectra of dyestuff DYE-1, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
(1) mensuration of solid film uv-visible absorption spectra
5mg dyestuff DYE-1 is dissolved in the 5ml methylene dichloride, evenly is applied on 100mm * 100mm quartz plate, its uv-visible absorption spectra is measured with UV-Vis 260 type ultraviolet-visible spectrometers in dry back, and to get maximum absorption wavelength be 578nm.
(2) mensuration of solubleness in 4-methyl-4-hydroxyl-2 pentanone
(3g＞ml＞2g) dyestuff DYE-1 is dissolved in 10ml 4-methyl-4-hydroxyl-2 pentanone and forms supersaturated solution with mlg, filter then this solution collect dissolving dye m2g not, according to formula: it is 1.2% that solubleness (g/ml)=(ml-m2) * 100%/10 calculates solubleness.
(3) mensuration of decomposition temperature
Dyestuff DYE-1 about 10mg is measured its thermogravimetric curve on Dupont 1090 thermal gravimetric analyzers, obtaining decomposition temperature is 393 ℃.
Embodiment 2
Dyestuff DYE-2's is synthetic:
With the 8-quinolylamine among 2-amino-4-methylthiazol replacement embodiment 1, other condition is identical with embodiment 1.M.p.137-140 ℃, azoic dyestuff yield: 60%.
1H-NMR(CDCl
3)(ppm)：1.35(s，9H)，1.45(s，9H)，2.59(s，3H)，7.00(s，1H)，7.55(s，1H)，7.67(s，1H)。
The metal complex azo dye yield: 80%, ESI:719.1 (M
+).
The pure solid film uv-visible absorption spectra of dyestuff DYE-2, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-2 replacement embodiment 1, other condition is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 622nm; Solubleness is 6.8%; Decomposition temperature is 315 ℃.
Embodiment 3
Dyestuff DYE-3's is synthetic:
With the 8-quinolylamine among 2-amino-4-(4 '-nitrophenyl) thiazole replacement embodiment 1, other condition is identical with embodiment 1.The azoic dyestuff yield: 65%, m.p.215-218 ℃.
1H-NMR(CDCl
3)(ppm)：1.38(s，9H)，1.47(s，9H)，7.58(s，1H)，7.72(s，1H)，7.76(s，1H)，8.15(d，2H)， 8.34(d，2H)。
The metal complex azo dye yield: 85%, ESI:933.1 (M
+).
The pure solid film uv-visible absorption spectra of dyestuff DYE-3, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-3 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 629nm; Solubleness is 4.75%, and decomposition temperature is 365 ℃.
Embodiment 4
Dyestuff DYE-4's is synthetic:
With 2-amino-1,3, the 4-thiadiazoles replaces the 8-quinolylamine among the embodiment 1, and other is identical with embodiment 1.
The azoic dyestuff yield: 70%, m.p.188-190 ℃.
1H-NMR(CDCl
3)(ppm)：1.37(s，9H)，1.46(s，9H)，7.60(s，1H)，7.70(s，1H)，9.12(s，1H)。
The metal complex azo dye yield: 87%, ESI:693.0 (M
+).
The pure solid film uv-visible absorption spectra of dyestuff DYE-4, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-4 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 613nm; Solubleness is 1.16%, and decomposition temperature is 287 ℃.
Embodiment 5
Dyestuff DYE-5's is synthetic:
With 2-amino-5-methyl isophthalic acid, 3, the 4-thiadiazoles replaces the 8-quinolylamine among the embodiment 1, and other is identical with embodiment 1.
The azoic dyestuff yield: 68%, m.p.157-160 ℃.
1H-NMR(CDCl
3)(ppm)：1.36(s，9H)，1.45(s，9H)，2.84(s，3H)，7.58(s，1H)，7.68(s，1H)。
The metal complex azo dye yield: 85%, ESI:743.2 (M
++ Na).
The pure solid film uv-visible absorption spectra of dyestuff DYE-5, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-5 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 616nm; Solubleness is 6.10%, and decomposition temperature is 305 ℃.
Embodiment 6
Dyestuff DYE-6's is synthetic:
With 2-amino-1,3, the 4-thiadiazoles replaces the 8-quinolylamine among the embodiment 1, replaces 2 among the embodiment 1 with p-tert-butylphenol, the 4-DI-tert-butylphenol compounds, and other is identical with embodiment 1.The azoic dyestuff yield: 62%, m.p.132-135 ℃.
1H-NMR(CDCl
3)(ppm)：1.38(s，9H)，7.08(d，1H)，7.58(d，1H)，7.88(s，1H)，9.14(s，1H)。
The metal complex azo dye yield: 83%, ESI:581.3 (M
+).
The pure solid film uv-visible absorption spectra of dyestuff DYE-6, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-6 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 610nm; Solubleness is 1.22%, and decomposition temperature is 318 ℃.
Embodiment 7
Dyestuff DYE-7's is synthetic:
8-quinolylamine with among 2-amino-4-(4 '-nitrophenyl) thiazole replacement embodiment 1 replaces 2 among the embodiment 1 with p-tert-butylphenol, the 4-DI-tert-butylphenol compounds, and other is identical with embodiment 1.The azoic dyestuff yield: 68%, m.p.182-185 ℃.
1H-NMR(CDCl
3)(ppm)：1.39(s，9H)，7.06(d，1H)，7.55(d，1H)，7.79(s，1H)，7.89(s，1H)，8.16(d，2H)，8.35(d，2H)。
The metal complex azo dye yield: 88%, ESI:843.1 (M
++ Na).
The pure solid film uv-visible absorption spectra of dyestuff DYE-7, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-7 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 618nm; Solubleness is 2.08%, and decomposition temperature is 345 ℃.
Embodiment 8
Dyestuff DYE-8's is synthetic:
With 2-amino-5-methyl isophthalic acid, 3, the 4-thiadiazoles replaces the 8-quinolylamine among the embodiment 1, replaces 2 among the embodiment 1 with p-tert-butylphenol, the 4-DI-tert-butylphenol compounds, other is identical with embodiment 1.The azoic dyestuff yield: 75%, m.p.123-125 ℃.
1H-NMR(CDCl
3)(ppm)：1.37(s，9H)，2.86(s，3H)，7.04(d，1H)，7.55(d，1H)，7.85(s，1H)。
The metal complex azo dye yield: 88%, ESI:609.1 (M
+).
The pure solid film uv-visible absorption spectra of dyestuff DYE-8, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-8 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 612nm; Solubleness is 2.50%, and decomposition temperature is 340 ℃.
Embodiment 9
Dyestuff DYE-9's is synthetic:
Synthesizing of azoic dyestuff:
2.58g2-methoxyl group-5-(N, N ,-diethyl sulfoamido) aniline is dissolved in the solution of being made up of 2.5ml37% hydrochloric acid and 20ml water, is cooled to-5 ℃-0 ℃.The 0.7g Sodium Nitrite is dissolved in the 15ml water, is cooled to-5 ℃-0 ℃.Under stirring state sodium nitrite solution is slowly joined in the amine aqueous solution, this process approximately needs 20 minutes, adds the back and continues to stir 1 hour.In whole process, keep temperature-5 ℃-0 ℃.
With 2.1g2, the 4-DI-tert-butylphenol compounds is dissolved in the 30ml ethanol, regulates pH=10-12 with dilute sodium hydroxide, is cooled to-5 ℃-0 ℃.Under agitation slowly diazonium liquid is added wherein, this process approximately needs 30 minutes.Adding the back continues to stir 3 hours.Whole process remains pH=10-12, temperature-5 ℃-0 ℃.Reaction finishes the back and regulates pH=6-7 with dilute hydrochloric acid, separates out a large amount of red solid.Solid collected by filtration, oven drying at low temperature.Get the orange red solid of 4.2g, yield 90% with ethyl alcohol recrystallization.m.p.153℃-154℃。
1H-NMR(CDCl
3)(ppm)：1.15(t，6H)，1.39(s，9H)，1.47(s，9H)，3.27(m，4H)，7.16(d，1H)，7.46(s，1H)，7.81(s，1H)，7.86(d，1H)，8.30(s，1H)。
Synthesizing of metal complex azo dye:
The 2.8g azoic dyestuff is dissolved among the 50mlDMF, is heated to backflow.0.67g six hydrated chromium trichlorides are dissolved among the 20mlDMF, slowly join above-mentioned dye solution, add the back and continue to reflux 6 hours.With the DMF pressure reducing and steaming, collect solid, drying.The solid ethyl alcohol recrystallization gets the 2.6g black crystals, yield 88%.ESI：971.2(M
+)。
The pure solid film uv-visible absorption spectra of dyestuff DYE-9, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-9 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 557nm; Solubleness is 2.58%, and decomposition temperature is 281 ℃.
Embodiment 10
Dyestuff DYE-10's is synthetic:
With 2-methoxyl group-5-(N, the N ,-diethyl sulfoamido) aniline among 2-methoxyl group-4-N-methyl-p-nitroaniline replacement embodiment 9, other is identical with embodiment 9.The azoic dyestuff yield: 89%, m.p.216-217 ℃.
1H-NMR(CDCl
3)(ppm)：1.39(s，9H)，1.48(s，9H)，4.28(s，3H)，7.36(s，1H)，7.60(s，1H)，7.79(s，1H)，8.07(d，1H)，8.10(d，1H)。
The metal complex azo dye yield: 92%, ESI:792.3 (M
+).
The pure solid film uv-visible absorption spectra of dyestuff DYE-10, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-10 replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 623nm; Solubleness is 14.80%, and decomposition temperature is 263 ℃.
The comparative example
Dyestuff DYE-C's is synthetic:
The synthetic method reference Mol.Cryst.Liq.Cryst.2001 of dyestuff DYE-C, 371:305-308.ESI：761.1(M
+)。
The pure solid film uv-visible absorption spectra of dyestuff DYE-C, the mensuration of solubleness and decomposition temperature in 4-methyl-4-hydroxyl-2 pentanone:
With the dyestuff DYE-1 among the dyestuff DYE-C replacement embodiment 1, other is identical with embodiment 1, and measurement result is as follows: maximum absorption wavelength is 552nm; Solubleness is 0.81%, and decomposition temperature is 300 ℃.
Claims (6)
1, a kind of DVD-R CD high-dissolvability metal complex azo dye has following general structure:
In the formula: A is for being substituted with the group that contains reactive hydrogen or aromatic nucleus or its substitutive derivative of methoxyl group at the azo-group ortho position; Or comprise heterocycle or its substitutive derivative of an energy and the nitrogen-atoms of complexing of metal ion at least; R is hydrogen or C
1～C
4Alkyl; M is a nickel, chromium, cobalt, copper, iron, manganese or zinc; M=1 or 2;
Wherein: the substituting group of aromatic nucleus or heterocyclic substitutive derivative is a nitro, halogen atom, carboxyl, sulfonic group, sulfonamido, aromatic base and/or C
1～C
4Alkyl.
2, compound according to claim 1 is characterized in that A is pyridine, thiazole, thiadiazoles, benzothiazole, quinoline or imidazoles, or its substitutive derivative, wherein: substituting group is a nitro in the substitutive derivative, halogen atom, carboxyl, sulfonic group, sulfonamido, aromatic base and/or C
1～C
4Alkyl.
3, as compound as described in the claim 2, it is characterized in that A is quinoline, thiazole or thiadiazoles, or its substitutive derivative, wherein: substituting group is a nitro in the substitutive derivative, halogen atom, carboxyl, sulfonic group, sulfonamido, aromatic base and/or C
1～C
4Alkyl.
4, as compound as described in the claim 3, it is characterized in that M is nickel or chromium.
5, compound according to claim 1 is characterized in that, A is for being substituted with the group that contains reactive hydrogen or the phenyl ring or the naphthalene nucleus of methoxyl group at the azo-group ortho position, or its substitutive derivative, wherein: the said group that contains reactive hydrogen is a hydroxyl, sulfydryl, amino, carboxyl, sulfonic group or sulfoamido, substituting group in the substitutive derivative is a nitro, halogen atom, carboxyl, sulfonic group, sulfonamido, aromatic base and/or C
1～C
4Alkyl.
6, as compound as described in the claim 5, it is characterized in that M is nickel or chromium.
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Citations (4)
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|---|---|---|---|---|
| CN1103083A (en) * | 1993-07-02 | 1995-05-31 | 日本化药株式会社 | Copper complex azo compounds and dyeing methods using said compounds |
| CN1136056A (en) * | 1994-12-21 | 1996-11-20 | 希巴-盖吉股份公司 | Dye mixtures comprising 1:2 chromium complex dyes, and 1:2 chromium complex dyes |
| WO2000009615A1 (en) * | 1998-08-14 | 2000-02-24 | Clariant Finance (Bvi) Limited | 1:2 chromium complex dyes, their production and use |
| CN1251376A (en) * | 1998-10-15 | 2000-04-26 | 拜尔公司 | Novel metal matches pigment |
-
2003
- 2003-05-16 CN CNB031169430A patent/CN100334158C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103083A (en) * | 1993-07-02 | 1995-05-31 | 日本化药株式会社 | Copper complex azo compounds and dyeing methods using said compounds |
| CN1136056A (en) * | 1994-12-21 | 1996-11-20 | 希巴-盖吉股份公司 | Dye mixtures comprising 1:2 chromium complex dyes, and 1:2 chromium complex dyes |
| WO2000009615A1 (en) * | 1998-08-14 | 2000-02-24 | Clariant Finance (Bvi) Limited | 1:2 chromium complex dyes, their production and use |
| CN1251376A (en) * | 1998-10-15 | 2000-04-26 | 拜尔公司 | Novel metal matches pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1454937A (en) | 2003-11-12 |
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