Patent Application
20080081286
The optical information recording medium and azo-metal complex dye of the present invention are described in detail below.
The optical information recording medium of the present invention has at least one recording layer on a substrate, and information can be recorded on the recording layer. It is preferred that the optical information recording medium further has a light reflection layer and a protective layer.
The recording layer in the optical information recording medium contains at least one particular azo-metal complex dye.
The azo-metal complex dye of the present invention is described below. The azo-metal complex dye is prepared by reacting an azo dye with a metal ion (which may be a metal oxide ion), to coordinate the azo dye to the metal ion.
Examples of the metal ions include ions of Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Ba, Pr, Eu, Yb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and Th. Preferred among them are ions of transition metals. The transition metals are elements of Groups IIIa to VIII and Ib of the Periodic Table of Elements, which have an incomplete d-electron shell. The transition metal is not particularly limited, and preferably Mn, Fe, Co, Ni, Cu, Zn, Cr, Ru, Rh, Pd, Ir, Pt, or Re, more preferably Cr, Mn, Fe, Co, Ni, Cu, or Zn, further preferably Mn, Fe, Co, Ni, Cu, or Zn, particularly preferably Fe, Co, Ni, or Cu.
The metal ion is preferably divalent or trivalent, more preferably divalent. Examples of the divalent or trivalent metal ions include Mn2+, Fe2+, Fe3+, Co2+, Co3+, Ni2+, Ni3+, Cu2+, Zn2+, Cr3+, Ru2+, Rh3+, Pd2+, Ir3+, Pt2+, and Re+. Preferred among them are Mn2+, Fe2+, Fe3+, Co2+, Co3+, Ni2+, Ni3+, Cu2+, and Zn2+, more preferred are Mn2+, Fe2+, Co2+, Co3+, Ni2+, Cu2+, and Zn2+, and further preferred are Fe2+, Co2+, Co3+, Ni2+, Ni3+, and Cu2+. In the present invention, Cu2+is particularly preferred from the viewpoints of the light fastness and the recording/reproducing properties.
In conventional azo-metal complex dyes for optical information recording media, Ni ions and Co ions have been more widely used than Cu ions from the viewpoint of the light fastness. However, the Cu ions are superior to the Ni ions and Co ions in terms of toxicity to the environment and human health. It is especially significant to use low-toxic metal ions such as Cu ions, Zn ions, and Fe ions for expanding the use of the optical information recording media and the azo-metal complex dyes.
Although the azo dye shown above is in the azo form in the azo-hydrazone tautomeric equilibrium, the azo dye may be in the hydrazone form. In the present invention, the dye in the hydrazone form is considered to be equivalent to that in the azo form.
Then, the general formulae (1-1) and (1-2) are described below.
R6 to R8 independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, alkyl groups including cycloalkyl groups and bicycloalkyl groups, alkenyl groups including cycloalkenyl groups and bicycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclyloxy groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, amino groups including anilino groups, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclylthio groups, sulfamoyl groups, a sulfo group, alkyl or aryl sulfinyl groups, alkyl or aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclyl azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups.
More specifically, examples of the substituents of R6 to R8 include halogen atoms such as chlorine, bromine, and iodine atoms; alkyl groups, which may be linear, branched, or cyclic and may be substituted or unsubstituted, including noncyclic alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl groups), cycloalkyl groups (preferably substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl and 4-n-dodecylcyclohexyl groups), bicycloalkyl groups (preferably substituted or unsubstituted, monovalent bicycloalkyl groups having 5 to 30 carbon atoms provided by eliminating one hydrogen atom from bicycloalkanes having 5 to 30 carbon atoms, such as bicyclo[1,2,2]heptane-2-yl and bicyclo[2,2,2]octane-3-yl groups), and polycyclic alkyl groups having more cyclic structures such as tricycloalkyl groups, alkyl groups in the flowing substituents (e.g. alkyl groups in alkylthio groups) having the same meanings; alkenyl groups, which may be linear, branched, or cyclic and may be substituted or unsubstituted, including noncyclic alkenyl groups (preferably substituted or unsubstituted alkyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, and oleyl groups), cycloalkenyl groups (preferably substituted or unsubstituted, monovalent cycloalkenyl groups having 3 to 30 carbon atoms provided by eliminating one hydrogen atom from cycloalkenes having 3 to 30 carbon atoms, such as 2-cyclopentene-1-yl and 2-cyclohexene-1-yl groups), and bicycloalkenyl groups (preferably substituted or unsubstituted, monovalent bicycloalkenyl groups having 5 to 30 carbon atoms provided by eliminating one hydrogen atom from bicycloalkenes having a double bond, such as bicyclo[2,2,1]hept-2-ene-1-yl and bicyclo[2,2,2]oct-2-ene-4-yl groups); alkynyl groups (preferably substituted or unsubstituted alkynyl groups having 2 to 30 carbon atoms, such as ethynyl, propargyl, and trimethylsilylethynyl groups); aryl groups (preferably substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphtyl, m-chlorophenyl, and o-hexadecanoylaminophenyl groups); heterocyclic groups (preferably monovalent groups provided by eliminating one hydrogen atom form 5- or 6-membered, substituted or unsubstituted, aromatic or nonaromatic, heterocyclic compounds, more preferably 5- or 6-membered aromatic heterocyclic groups having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl groups); a cyano group; a hydroxyl group; a nitro group; a carboxyl group; alkoxy groups (preferably substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, and 2-methoxyethoxy groups); aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy groups); silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms, such as trimethylsilyloxy and t-butyldimethylsilyloxy groups); heterocyclyloxy groups (preferably substituted or unsubstituted heterocyclyloxy groups having 2 to 30 carbon atoms, such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy groups); acyloxy groups (preferably a formyloxy group, substituted or unsubstituted alkylcarbonyloxy groups having 2 to 30 carbon atoms, and substituted or unsubstituted arylcarbonyloxy groups having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy groups); carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms, such as N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy groups); alkoxycarbonyloxy groups (preferably substituted or unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, and n-octylcarbonyloxy groups); aryloxycarbonyloxy groups (preferably substituted or unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and p-n-hexadecyloxyphenoxycarbonyloxy groups); amino groups (preferably an amino group, substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted anilino groups having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, and diphenylamino groups); acylamino groups (preferably a formylamino group, substituted or unsubstituted alkylcarbonylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, and 3,4,5-tri-n-octyloxyphenylcarbonylamino groups); aminocarbonylamino groups (preferably substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms, such as carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino groups); alkoxycarbonylamino groups (preferably substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino groups); aryloxycarbonylamino groups (preferably substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-n-octyloxyphenoxycarbonylamino groups); sulfamoylamino groups (preferably substituted or unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms, such as sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino groups); alkyl or aryl sulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino groups); a mercapto group; alkylthio groups (preferably substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as methylthio, ethylthio, and n-hexadecylthio groups); arylthio groups (preferably substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, and m-methoxyphenylthio groups); heterocyclylthio groups (preferably substituted or unsubstituted heterocyclylthio groups having 2 to 30 carbon atoms, such as 2-benzothiazolylthio and 1-phenyltetrazole-5-ylthio groups); sulfamoyl groups (preferably substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, and N-(N′-phenylcarbamoyl)sulfamoyl groups); a sulfo group; alkyl or aryl sulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl groups); alkyl or aryl sulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, and p-methylphenylsulfonyl groups); acyl groups (preferably a formyl group, substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl groups having 7 to 30 carbon atoms, and substituted or unsubstituted heterocyclylcarbonyl groups having 4 to 30 carbon atoms and a heterocycle containing a carbon atom bonded to a carbonyl group, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, and 2-furylcarbonyl groups); aryloxycarbonyl groups (preferably substituted or unsubstituted aryloxycarbonyl groups having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-t-butylphenoxycarbonyl groups); alkoxycarbonyl groups (preferably substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and n-octadecyloxycarbonyl groups); carbamoyl groups (preferably substituted or unsubstituted carbamoyl groups having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl groups); aryl or heterocyclyl azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms and substituted or unsubstituted heterocyclylazo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazole-2-yl azo groups); imide groups (preferably N-succinimide and N-phthalimide groups); phosphino groups (preferably substituted or unsubstituted phosphino groups having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino groups); phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl groups); phosphinyloxy groups (preferably substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy groups); phosphinylamino groups (preferably substituted or unsubstituted phosphinylamino groups having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino and dimethylaminophosphinylamino groups); and silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl groups).
A hydrogen atom in the above functional groups may further be substituted by the functional groups. Examples of such substituents include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups, and arylsulfonylaminocarbonyl groups. Specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.
R6 is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, further preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a branched alkyl group having 3 to 6 carbon atoms, more preferably a tertiary alkyl group having 4 to 6 carbon atoms.
Each of R7 and R8 is preferably a substituent. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
Q represents a carbocyclic group or a heterocyclic group. Q has a ring or substituent containing an atom capable of forming a bond with the metal ion, such as an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.
The carbocyclic group of Q is preferably a phenyl group. In this case, Q has a substituent containing an atom capable of forming a bond with the metal ion. Q may have a further substituent in addition to the substituent containing an atom capable of forming a bond with the metal ion. It is preferred that Q has the further substituent from the viewpoint of increasing solubility. The further substituent is not particularly limited, and is preferably a group other than a hydroxyl group, alkyloxy groups, aryloxy groups, a thiol group, alkylthio groups, arylthio groups, amino groups, alkylamino groups, and arylamino groups. The further substituent is preferably a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkoxysulfonyl group having 1 to 10 carbon atoms, more preferably a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, further preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms.
In a case where Q is a heterocyclic group, Q has a ring or substituent containing an atom capable of forming a covalent bond with the metal ion. The ring of Q is not particularly limited, and may be a pyrazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, a 1,2,4-thiadiazole ring, a 1,3,4-thiadiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, or the like.
Q preferably has a substituent. The substituent on Q is not particularly limited, and examples thereof include those of R6 to R8, and R1, R2, and R11 to R14 to be hereinafter described.
Among the general formulae (1-1) and (1-2), the general formula (1-1) is preferred from the viewpoint of recording properties.
Specific examples of the azo dyes represented by the general formula (1-1) are illustrated below without intention of restricting the scope of the present invention.
Specific examples of the azo dyes represented by the general formula (1-2) are illustrated below without intention of restricting the scope of the present invention.
The general formula (A) is described in detail below. In the general formula (A), M represents a metal ion or a metal oxide ion, and the meanings and preferred embodiments thereof are the same as those of the above-mentioned metal ion or metal oxide ion.
L′ represents a ligand. The ligand is an atom or an atomic group that is bonded to the metal ion. The ligand may be selected from the preferred examples to be hereinafter described and those described in H. Yersin, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, 1987, Akio Yamamoto, “Yuki Kinzoku Kagaku Kiso to Oyo (Organometallic Chemistry, Foundation and Application)”, Shokabo Publishing Co., Ltd., 1982, and the like. Specific examples of the ligands are described below.
In L′, an atom coordinating to M is preferably a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a halogen atom, more preferably a nitrogen atom, an oxygen atom, or a halogen atom, further preferably a nitrogen atom or an oxygen atom, particularly preferably a nitrogen atom.
When L′ is coordinated to M, the bond formed between M and L′ may be a covalent bond (a bond) or a coordinate bond. Thus, L′ may be an anionic ligand or a neutral ligand.
The ligand of L′ having a nitrogen atom coordinating to M is not particularly limited, and examples thereof include nitrogen-containing, aromatic heterocycle ligands such as pyridine ligands, pyrazine ligands, pyrimidine ligands, pyridazine ligands, triazine ligands, thiazole ligands, oxazole ligands, pyrrole ligands, imidazole ligands, pyrazole ligands, triazole ligands, oxadiazole ligands, thiadiazole ligands, condensed ligands thereof (e.g. quinoline ligands, benzoxazole ligands, benzimidazole ligands), and tautomers thereof; amine ligands such as ammonia, methylamine, dimethylamine, diethylamine, dibenzylamine, triethylamine, piperidine, piperazine, morpholine, and arylamines; aniline ligands such as aniline, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, diphenylamine, N-acylanilines, and N-alkylsulfonylanilines; imine ligands; nitrile ligands such as an acetonitrile ligand; isonitrile ligands such as a t-butylisonitrile ligand; and amide ligands such as a dimethylformamide ligand and a dimethylacetamide ligand. These ligands may have a substituent.
The ligand of L′ having an oxygen atom coordinating to M is not particularly limited, and examples thereof include alcohol ligands, preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 10 carbon atoms, such as monovalent anion ligands provided by eliminating a proton from methanol, ethanol, butanol, 2-ethylhexanol, or the like; aryloxy ligands, preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as monovalent anion ligands provided by eliminating a proton from phenol, 1-naphthol, 2-naphthol, or the like; diketone ligands such as an acetylacetone ligand; silyloxy ligands, preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, particularly preferably having 3 to 24 carbon atoms, such as a trimethylsilyloxy ligand and a triphenylsilyloxy ligand; ether ligands including cyclic ether ligands; carboxylic acid ligands; sulfonic acid ligands; aqua ligands; and O2 ligands. These ligands may have a substituent.
The ligand of L′ having a sulfur atom coordinating to M is not particularly limited, and examples thereof include alkylthiol ligands, preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as monovalent anion ligands provided by eliminating a proton from butanethiol or the like; arylthiol ligands, preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as thiophenol; and thioether ligands. These ligands may have a substituent.
The ligand of L′ having a phosphorus atom coordinating to M is not particularly limited, and examples thereof include alkylphosphine ligands, preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, such as methylphosphine, dimethylphosphine, diethylphosphine, and dibenzylphosphine; and arylphosphine ligands, preferably having 3 to 30 carbon atoms, more preferably having 4 to 20 carbon atoms, particularly preferably having 5 to 10 carbon atoms, such as phenylphosphine, diphenylphosphine, and pyridylphosphine. These ligands may have a substituent.
The ligand of L′ coordinating to M may be a halogen ligands such as a chlorine ligand, a fluorine ligand, a bromine ligand, and an iodine ligand.
When M is Cu2+ or Zn2+, L′ is preferably a monovalent or divalent, anionic ligand. Examples of such anionic ligands coordinating to Cu2+ include halogen ligands, carboxylic acid ligands, silyloxy ligands, aryloxy ligands, anionic anilino ligands, anionic pyrazole ligands, anionic imidazole ligands, and anionic triazole ligands. Preferred among them are halogen ligands, carboxylic acid ligands having 2 to 10 carbon atoms, anionic anilino ligands, anionic pyrazole ligands, and anionic imidazole ligands, more preferred are halogen ligands and carboxylic acid ligands having 2 to 10 carbon atoms, and further preferred are carboxylic acid ligands having 2 to 10 carbon atoms. These ligands other than the halogen ligands may be an azo dye component such as a coupler component or a diazo component.
n is an integer of 1 to 4, preferably 1 or 2.
m is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1.
r is 1 or 2, preferably 1.
k′ is a number within the range of 0<k′≦4, obtained by dividing the negative valence of (L2−)n(L′)m(M)r in the general formula (A) by p.
In the general formula (A), Xp+ represents a p-valent cation. Examples of the cations of Xp+ include ammonium cations, alkaline metal ions, and alkaline earth metal ions such as Mg2+, and the ammonium cations include ammonium cations represented by the following general formula (X) and di- or more-valent ammonium cations represented by the following general formula (XX).
The cation is preferably an ammonium cation represented by the general formula (X) or (XX).
The general formula (X) is described below. R21 to R24 independently represent a hydrogen atom, an alkyl group, or an aryl group. R21 to R24 may be connected to each other by a linking group.
More specifically, R21 to R24 may be selected respectively from alkyl groups, which may be linear, branched, or cyclic and may be substituted or unsubstituted, including noncyclic alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl groups), cycloalkyl groups (preferably substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl and 4-n-dodecylcyclohexyl groups), bicycloalkyl groups (preferably substituted or unsubstituted, monovalent bicycloalkyl groups having 5 to 30 carbon atoms provided by eliminating one hydrogen atom from bicycloalkanes having 5 to 30 carbon atoms, such as bicyclo[1,2,2]heptane-2-yl and bicyclo[2,2,2]octane-3-yl groups), and polycyclic alkyl groups having more cyclic structures such as tricycloalkyl groups, alkyl groups in the flowing substituents (e.g. alkyl groups in alkylthio groups) having the same meanings; and aryl groups (preferably substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphtyl, m-chlorophenyl, and o-hexadecanoylaminophenyl groups). These groups may further have a substituent.
It is preferred that at least one of R21 to R24 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
The general formula (XX) is described below. R25 to R27 independently represent a hydrogen atom, an alkyl group or an aryl group. n11 represents an integer of 2 to 10. A plurality of R25's, R26's, R27's may be the same or different ones respectively. L represents an alkyl or aryl linking group, which may contain —O— or —S—. R25 to R27 may be connected to each other by a linking group. R25 to R27 and L may further have a substituent.
It is preferred that at least one of R25 to R27 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
n11 is preferably an integer of 2 to 8, more preferably an integer of 2 to 4, further preferably 2 or 3, particularly preferably 2.
L is preferably a substituted or unsubstituted alkyl linking group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl linking group having 1 to 5 carbon atoms, further preferably a substituted or unsubstituted alkyl linking group having 1 to 3 carbon atoms.
Specific examples of the organic cations are illustrated below without intention of restricting the scope of the present invention.
It is preferred that the organic cation is an alkyl ammonium cation from the viewpoint of solubility in coating liquid solvents. Among the above alkyl ammonium cations, more preferred are cations having a positive charge on a nitrogen atom in a nitrogen-containing heterocycle such as (X-4), (X-7), and (X-11) and divalent cations such as (X-3), (X-4), (X-9), and (X-10), and further preferred are divalent cations. p is preferably 1 or 2, more preferably 2.
L2− represents a divalent azo dye anion derived by eliminating two hydrogen atoms from the azo dye represented by the general formula (1-3) or (1-4).
Then, the general formulae (1-3) and (1-4) are described below. R6 to R8 independently represent a hydrogen atom or a substituent. R6 to R8 in the general formulae (1-3) and (1-4) have the same meanings and preferred embodiments as those in the general formulae (1-1) and (1-2).
Although the azo dye of the general formula (1-3) or (1-4) shown above is in the azo form in the azo-hydrazone tautomeric equilibrium, the azo dye may be in the hydrazone form. In the present invention, the dye in the hydrazone form is considered to be equivalent to that in the azo form.
Q′ represents a carbocyclic group or a heterocyclic group. Q′ has a ring or substituent containing an atom capable of forming a covalent bond with the metal ion. One hydrogen atom of the substituent of Q′ may be removed to form a covalent bond between the substituent and the metal ion. Examples of such substituents that release a hydrogen atom to form a covalent bond with the metal ion include a hydroxyl group, a thiol group, amino groups, a carboxyl group, and a sulfonic acid group.
Preferred examples of the substituents of Q′ containing an atom forming a covalent bond with the metal ion include a hydroxyl group; amino groups (preferably an amino group, substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted anilino groups having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, and diphenylamino groups); acylamino groups (preferably a formylamino group, substituted or unsubstituted alkylcarbonylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, and 3,4,5-tri-n-octyloxyphenylcarbonylamino groups); aminocarbonylamino groups (preferably substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms, such as carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino groups); alkoxycarbonylamino groups (preferably substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino groups); aryloxycarbonylamino groups (preferably substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-n-octyloxyphenoxycarbonylamino groups); sulfamoylamino groups (preferably substituted or unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms, such as sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino groups); and alkyl or aryl sulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino groups). When the substituent forming a covalent bond with the metal ion is an amino group having a substituent, the amino group is preferably a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, or a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, further preferably a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, particularly preferably a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms or a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms.
Q′ may have a further substituent in addition to the substituent containing an atom forming a covalent bond with the metal ion. It is preferred that Q′ has the further substituent from the viewpoint of increasing solubility. The examples and preferred embodiments of the further substituents on Q′ are the same as those on Q.
When Q′ is a heterocyclic group, Q′ has a ring or substituent containing an atom capable of forming a covalent bond with the metal ion.
Examples of the rings forming a covalent bond with the metal ion include those represented by the formulae (q-1) to (q-4) to be hereinafter described for the general formula (2-1).
The substituent forming a covalent bond with the metal ion may be such as described above in the case where Q′ is a carbocyclic group.
In a case were Q′ is a heterocyclic group having a substituent containing an atom capable of forming a covalent bond with the metal ion, examples of heterocycles of Q′ are the same as those of Q in the general formulae (1-1) and (1-2). In this case, the heterocyclic group of Q′ preferably contains a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, or a triazine ring.
Q′ preferably has a substituent, and the substituent is not particularly limited. Examples of the substituents on Q′ are the same as those of R6 to R8.
Q′ preferably contains a nitrogen-containing heterocycle formed by Q2 to be hereinafter described.
Among the general formulae (1-3) and (1-4), the general formula (1-3) is preferred from the viewpoint of light fastness.
Specific examples of the azo dyes represented by the general formula (1-3) are illustrated below without intention of restricting the scope of the present invention.
Specific examples of the azo dyes represented by the general formula (1-4) are illustrated below without intention of restricting the scope of the present invention.
The azo-metal complex dye of the general formula (A) is preferably represented by the general formula (2-1) or (3-1).
The general formula (2-1) is described in detail below. M represents a metal ion (or a metal oxide ion), and the meanings and preferred embodiments of M in the general formulae (2-1) and (3-1) are the same as those of M in the general formula (A).
The meanings and preferred embodiments of p in the general formula (2-1) are the same as those of p in the general formula (A).
In the general formula (2-1), q is an integer of 1 to 4, preferably 1 or 2.
n1 is an integer of 1 to 3, preferably 1 or 2.
n2 is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1.
n3 is a number within a range of 0<n3≦4, obtained by q/p.
Q2 represents an atomic group forming a nitrogen-containing heterocycle. The nitrogen-containing heterocyclic group formed by Q2 is preferably represented by any one of the following structural formulae (q-1) to (q-4), more preferably represented by the formula (q-1) or (q-2), and further preferably represented by the formula (q-1).
In the formulae (q-1) to (q-4), each asterisk * represents a position at which the heterocyclic group is bonded to —N═N—, each double asterisk ** represents a position at which the heterocyclic group is covalent-bonded to M, and each of R1, R2, and R11 to R14 represents a hydrogen atom or a substituent.
R1, R2, and R11 to R14 independently represent a hydrogen atom or a substituent. It is preferred from the viewpoint of solubility that each of R1, R2 and R11 to R14 is a substituent. The substituent is not particularly limited, and examples thereof are the same as those of R6 to R8.
Each of R1, R11, and R12 is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkyloxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkylaminocarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted arylaminocarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, or a cyano group, more preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkyloxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, or a cyano group, further preferably a substituted or unsubstituted alkyloxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, or a cyano group, and is particularly preferably a cyano group.
Each of R2, R13 and R14 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and is more preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms in view of solubility. The alkyl group is preferably a branched alkyl group having 3 to 6 carbon atoms, more preferably a tertiary alkyl group having 4 to 6 carbon atoms.
The meanings and preferred embodiments of R6 and R7 in the general formula (2-1) are the same as those of R6 and R7 in the general formula (1-1).
L1 represents a ligand. The ligand is an atom or an atomic group that is bonded to the metal ion. The ligand may be selected from the preferred examples to be hereinafter described and those described in H. Yersin, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, 1987, Akio Yamamoto, “Yuki Kinzoku Kagaku Kiso to Oyo (Organometallic Chemistry, Foundation and Application)”, Shokabo Publishing Co., Ltd., 1982, and the like. Specific examples of the ligands are described below.
In L1, an atom coordinating to M is preferably a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, more preferably a nitrogen atom or an oxygen atom, further preferably a nitrogen atom.
When L1 is coordinated to M, the bond formed between M and L1 may be a covalent bond or a coordinate bond.
The ligand of L1 having a nitrogen atom coordinating to M is not particularly limited, and examples thereof include nitrogen-containing, aromatic heterocycle ligands such as pyridine ligands, pyrazine ligands, pyrimidine ligands, pyridazine ligands, triazine ligands, thiazole ligands, oxazole ligands, pyrrole ligands, imidazole ligands, pyrazole ligands, triazole ligands, oxadiazole ligands, thiadiazole ligands, condensed ligands thereof (e.g. quinoline ligands, benzoxazole ligands, benzimidazole ligands), and tautomers thereof; amine ligands such as ammonia, methylamine, dimethylamine, diethylamine, dibenzylamine, triethylamine, piperidine, piperazine, morpholine, and arylamines; imine ligands; halogen ligands such as a chlorine ligand and a fluorine ligand; diketone ligands such as an acetylacetone ligand; nitrile ligands such as an acetonitrile ligand; a CO ligand; isonitrile ligands such as a t-butylisonitrile ligand; an aqua ligand; carboxylic acid ligands such as an acetic acid ligand; and amide ligands such as a dimethylformamide ligand and a dimethylacetamide ligand. These ligands may have a substituent.
The ligand of L1 having an oxygen atom coordinating to M is not particularly limited, and examples thereof include alcohol ligands, preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 10 carbon atoms, such as monovalent anion ligands provided by eliminating a proton from methanol, ethanol, butanol, 2-ethylhexanol, or the like; arylalcohol ligands, preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as monovalent anion ligands provided by eliminating a proton from phenol, 1-naphthol, 2-naphthol, or the like; silyloxy ligands, preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, particularly preferably having 3 to 24 carbon atoms, such as a trimethylsilyloxy ligand and a triphenylsilyloxy ligand; a carbonyl ligand; ether ligands including cyclic ether ligands; carboxylic acid ligands; sulfonic acid ligands; aqua ligands; and O2 ligands. These ligands may have a substituent.
The ligand of L1 having a sulfur atom coordinating to M is not particularly limited, and examples thereof include alkylthiol ligands, preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as monovalent anion ligands provided by eliminating a proton from butanethiol or the like; arylthiol ligands, preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as thiophenol; and thioether ligands. These ligands may have a substituent.
The ligand of L1 having a phosphorus atom coordinating to M is not particularly limited, and examples thereof include alkylphosphine ligands, preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, such as methylphosphine, dimethylphosphine, diethylphosphine, and dibenzylphosphine; and arylphosphine ligands, preferably having 3 to 30 carbon atoms, more preferably having 4 to 20 carbon atoms, particularly preferably having 5 to 10 carbon atoms, such as phenylphosphine, diphenylphosphine, and pyridylphosphine. These ligands may have a substituent.
L1 never represents the azo dye ligand shown in the general formula (2-1), and it is preferred that L1 is another azo dye ligand.
Specific examples of the azo-metal complex dyes represented by the general formula (2-1) are illustrated below without intention of restricting the scope of the present invention.
Specific examples of the azo-metal complex dyes having a center metal of Cu or Zn are illustrated below without intention of restricting the scope of the present invention.
Example Compound (M-13) is equivalent to Example Compounds (M-13′) and (M-13′), and this azo-metal complex dye may have any one of the resonance structures. Also the other azo-metal complex dyes having a center metal of Cu or Zn may have any resonance structure.
In addition, when the azo-metal complex dye of the general formula (2-1) containing Cu2+ as the metal ion M is dissolved in a solvent and analyzed by mass spectrometry (ESI-MS, MALDI-TOF-MS, etc.), also a complex having a structure different from the general formula (2-1) is also detected. Specifically, anions having different Cu2+/azo dye ligand ratios are detected, and a monovalent anion having the ratio of 2/2, a monovalent anion having the ratio of 3/2, and a divalent anion having the ratio of 5/4 are mainly detected. An anion having the ratio of 1/1 is detected in some cases, and when L′ is poor in coordinate bonding property, L′ is often eliminated from the anion. Further, in ESR analysis, the ligand number of the azo-metal complex dye varies depending on whether it is in the solid state or the liquid state. This is because the most stable structure of the azo-metal complex dye in the solid state is different from that in the liquid state, and thus ligand exchange proceeds easily in a solvent.
The general formula (3-1) is descrived below. The meanings and preferred embodiments of Q2, M, R6, R8, L1, n1 to n3, Xp+, p, and q in the general formula (3-1) are the same as those of Q2, M, R6, R7, L1, n1 to n3, Xp+, p, and q in the general formula (2-1).
Specific examples of the azo-metal complex dyes represented by the general formula (3-1) are illustrated below without intention of restricting the scope of the present invention.
The components of the optical information recording medium of the present invention are described below.
Embodiments (1) and (2) are described as preferred embodiments of the optical information recording medium according to the present invention.
Embodiment (1): An optical information recording medium containing a dye-containing WORM-type recording layer and a cover layer having a thickness of 0.01 to 0.5 mm disposed in this order on a substrate having a thickness of 0.7 to 2 mm.
Embodiment (2): An optical information recording medium containing a dye-containing WORM-type recording layer and a protective substrate having a thickness of 0.1 to 1.0 mm disposed in this order on a substrate having a thickness of 0.1 to 1.0 mm.
In Embodiment (1), it is preferred that the substrate has pregrooves with a track pitch of 50 to 500 nm, a groove width of 25 to 250 nm, and a groove depth of 5 to 150 nm. In Embodiment (2), it is preferred that the substrate has pregrooves with a track pitch of 200 to 600 nm, a groove width of 50 to 300 nm, a groove depth of 30 to 150 nm, and a wobble amplitude of 5 to 50 nm.
The optical information recording medium of Embodiment (1) has the substrate, the WORM-type recording layer, and the cover layer. A specific example of the optical information recording medium of Embodiment (1) is shown in
As shown in
The components are described below.
In Embodiment (1), the substrate 12 has pregrooves 34 (guide grooves) with particular track pitch, groove width (half width), groove depth, and wobble amplitude to be hereinafter described. The pregrooves 34 are formed in order to achieve a recording density higher than those of CD-R and DVD-R, and are suitable for optical information recording media using bluish purple laser lights.
The track pitch of the pregrooves 34 is 50 to 500 nm. The track pitch is preferably 420 nm or less, more preferably 370 nm or less, further preferably 330 nm or less. Further, the track pitch is preferably 100 nm or more, more preferably 200 nm or more, further preferably 260 nm or more. When the track pitch is 50 nm or more, the pregrooves can be formed accurately to prevent crosstalk. When the track pitch is 500 nm or less, high-density recording can be achieved.
The track pitch of the pregrooves is preferably 100 to 420 nm, more preferably 200 to 370 nm, further preferably 260 to 330 nm.
The groove width (the half width, which is a width at half the groove depth) of each pregroove 34 is 25 to 250 nm. The groove width is preferably 240 nm or less, more preferably 230 nm or less, further preferably 220 nm or less. Further, the groove width is preferably 50 nm or more, more preferably 80 nm or more, further preferably 100 nm or more. When the groove width of the pregroove 34 is 25 nm or more, the groove can sufficiently be transferred in a forming process, and the error rate can be reduced in a recording process. When the groove width is 250 nm or less, the groove can be sufficiently transferred in a forming process, and a pit formed in a recording process can be reduced to prevent crosstalk.
The groove width (the half width) of each pregroove is preferably 50 to 240 nm, more preferably 80 to 230 nm, further preferably 100 to 220 nm.
The groove depth of each pregroove 34 is 5 to 150 nm. The groove depth is preferably 85 nm or less, more preferably 80 nm or less, further preferably 75 nm or less. Further, the groove depth is preferably 10 nm or more, more preferably 20 nm or more, further preferably 28 nm or more. When the groove depth of the pregroove 34 is 5 nm or more, a sufficient recording modulation can be obtained. When the groove depth is 150 nm or less, a high reflectance can be obtained.
The groove depth of each pregroove is preferably 10 to 85 nm, more preferably 20 to 80 nm, further preferably 28 to 75 nm.
The groove inclination angle of each pregroove 34 is preferably 80° or less, more preferably 75° or less, further preferably 70° or less, particularly preferably 65° or less. Further, the groove inclination angle is preferably 20° or more, more preferably 30° or more, further preferably 40° or more.
When the groove inclination angle of the pregroove 34 is 20° or more, a sufficient tracking error signal amplitude can be obtained. When the groove inclination angle is 80° or less, excellent formability can be achieved.
In Embodiment (1), the WORM-type recording layer 14 may be formed by the steps of dissolving a dye in a solvent together with or without a binder, etc., to prepare a coating liquid, applying the coating liquid to the substrate or the light reflection layer 18, and drying the applied coating layer. The WORM-type recording layer 14 may have a single- or multi-layer structure, and the step of applying a coating liquid is repeatedly carried out to form such a multilayer structure.
The concentration of the dye in the coating liquid is generally 0.01% to 15% by mass, preferably 0.1% to 10% by mass, more preferably 0.5% to 5% by mass, most preferably 0.5% to 3% by mass.
Examples of the solvents for preparing the coating liquid include esters such as butyl acetate, ethyl lactate, and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and chloroform; amides such as dimethylformamide; hydrocarbons such as methylcyclohexane; ethers such as tetrahydrofuran, ethyl ether, and dioxane; alcohols such as ethanol, n-propanol, isopropanol, n-butanol, and diacetone alcohol; fluorine-containing solvents such as 2,2,3,3-tetrafluoro-1-propanol; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether.
The solvents may be used singly or as a mixture of two or more in view of the solubility of the dye. Various additives such as binders, antioxidants, UV absorbers, plasticizers, and lubricants may be added to the coating liquid in accordance with the purpose.
Examples of methods for applying the coating liquid include spray methods, spin coating methods, dipping methods, roll coating methods, blade coating methods, doctor roll methods, and screen printing methods. Preferred among them are spin coating methods.
In the applying step, the temperature of the coating liquid is preferably 23° C. to 50° C., more preferably 24° C. to 40° C., particularly preferably 23° C. to 50° C.
On a land 38 (a convex portion of the substrate 12), the thickness of the WORM-type recording layer 14 is preferably 300 nm or less, more preferably 250 nm or less, further preferably 200 nm or less, particularly preferably 180 nm or less. Further, the thickness is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, particularly preferably 7 nm or more.
On a groove 40 (a concave portion of the substrate 12), the thickness of the WORM-type recording layer 14 is preferably 400 nm or less, more preferably 300 nm or less, further preferably 250 nm or less. Further, the thickness is preferably 10 nm or more, more preferably 20 nm or more, further preferably 25 nm or more.
The ratio of the thickness of the WORM-type recording layer 14 on the land 38 to the thickness of the WORM-type recording layer 14 on the groove 40 is preferably 0.1 or more, more preferably 0.13 or more, further preferably 0.15 or more, particularly preferably 0.17 or more. The ratio is preferably less than 1, more preferably 0.9 or less, further preferably 0.85 or less, particularly preferably 0.8 or less.
An anti-fading agent may be added to the WORM-type recording layer 14 to increase the light fastness of the layer. In general, the anti-fading agent is a singlet oxygen quencher. The light fastness can be further improved by adding the singlet oxygen quencher in the present invention. The singlet oxygen quencher may be selected from those described in known publications such as patent publications.
Specific examples of the singlet oxygen quenchers are described in Japanese Laid-Open Patent Publication Nos. 58-175693, 59-81194, 60-18387, 60-19586, 60-19587, 60-35054, 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, 60-47069, 63-209995, and 4-25492; Japanese Patent Publication Nos. 1-38680 and 6-26028; Germany Patent No. 350399; Nippon Kagakukaishi, 1992, October issue, Page 1141; etc.
The ratio of the anti-fading agent such as the singlet oxygen quencher to the dye is generally 0.1% to 50% by mass, preferably 0.5% to 45% by mass, further preferably 3% to 40% by mass, particularly preferably 5% to 25% by mass.
In Embodiment (1), the cover layer 16 is formed on the WORM-type recording layer 14 or the barrier layer 20 as shown in
The cover layer 16 is not particularly limited as far as it is a transparent film, and preferred examples of the materials for the transparent film include acrylic resins such as polycarbonates and polymethyl methacrylates; vinyl chloride resins such as polyvinyl chlorides and vinyl chloride copolymers; epoxy resins; amorphous polyolefins; polyesters; and cellulose triacetates. More preferred among them are polycarbonates and cellulose triacetates.
The term “transparent” means that the transmittance of a light for recording and reproducing is 80% or more.
Various additives may be added to the cover layer 16 as far as they do not interfere with the advantageous effects of the present invention. For example, the cover layer 16 may contain a UV absorber for blocking out lights with wavelengths of 400 nm or less and/or a dye for blocking out lights with wavelengths of 500 nm or more.
The surface physical properties of the cover layer 16 are preferably such that the surface roughness is 5 nm or less as both the 2- and 3-dimensional roughness parameters.
It is preferred that the birefringence of the cover layer 16 is 10 nm or less from the viewpoint of property of concentrating a light used for recording and reproducing.
The thickness of the cover layer 16 may be determined depending on the wavelength of a laser light 46 for recording and reproducing and NA. In the present invention, the thickness is preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.12 mm.
The total thickness of the cover layer 16 and the adhesion layer or sticking layer 22 is preferably 0.09 to 0.11 mm, more preferably 0.095 to 0.105 mm.
A protective layer (such as a hard coat layer 44 shown in
To stick the cover layer 16 on the WORM-type recording layer 14 or barrier layer 20, the adhesion layer or sticking layer 22 may be formed between the layers.
The adhesion layer contains an adhesive, and preferred examples of the adhesives include UV curing resins, EB curing resins, and thermosetting resins.
In the case of using the UV curing resin as the adhesive, the UV curing resin may directly be applied onto the barrier layer. Alternatively, the UV curing resin may be dissolved in an appropriate solvent such as methyl ethyl ketone or ethyl acetate, and thus-obtained coating liquid may be added to a dispenser and applied therefrom to the barrier layer. It is preferred that the UV curing resin for the adhesion layer has a small cure shrinkage ratio from the viewpoint of preventing curling of the optical information recording medium. Examples of such UV curing resins include SD-640 available from Dainippon Ink and Chemicals, Inc.
Method for forming the adhesion layer is not particularly limited. The adhesion layer is preferably formed by the steps of applying an adhesive to a surface of the barrier layer 20 or the WORM-type recording layer 14 (a surface to be attached), placing the cover layer 16 thereon, spreading the adhesive between the surface and the cover layer 16 uniformly by spin coating, and hardening the adhesive.
The thickness of the adhesion layer is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, further preferably 1 to 30 μm.
The sticking layer contains a sticking agent, and examples thereof include acrylate-, rubber-, or silicone-based sticking agents. The acrylate-based sticking agents are preferred from the viewpoints of transparency and durability. The acrylate-based sticking agent is preferably a copolymer of a main component such as 2-ethylhexyl acrylate or n-butyl acrylate with a short-chain component and a crosslinking point component for increasing cohesion force. The short-chain component is an alkyl acrylate or methacrylate such as methyl acrylate, ethyl acrylate, or methyl methacrylate, and the crosslinking point component may be acrylic acid, methacrylic acid, an acrylamide derivative, maleic acid, hydroxylethyl acrylate, glycidyl acrylate, or the like. By appropriately selecting the mixing ratio and types of the main component, the short-chain component, and the crosslinking point component, the glass-transition temperature (Tg) and the crosslinking density of the sticking agent can be controlled.
Method for forming the sticking layer is not particularly limited, and the sticking layer may be formed by the steps of applying the sticking agent uniformly to a surface of the barrier layer 20 or the WORM-type recording layer 14 (a surface to be attached), placing the cover layer 16 thereon, and hardening the sticking agent. Alternatively, the sticking layer may be formed by the steps of applying the sticking agent uniformly to one surface of the cover layer 16 to form a sticking agent coating, sticking the coating on the surface, and hardening the coating.
A commercially-available sticking film containing a cover layer 16 and a sticking layer may be used in the present invention.
The thickness of the sticking layer is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, further preferably 10 to 30 μm.
The cover layer 16 may be formed by a spin coating method using a UV curing resin.
The optical information recording medium 10A of Embodiment (1) may have another layer in addition to the essential layers as far as it does not interfere with the advantageous effects of the present invention. Examples of such layers include a label layer having an image, formed on the back surface of the substrate 12 (the side opposite to the surface on which the WORM-type recording layer 14 is formed); a light reflection layer 18 (to be hereinafter described in detail), formed between the substrate 12 and the WORM-type recording layer 14; a barrier layer 20 (to be hereinafter described in detail), formed between the WORM-type recording layer 14 and the cover layer 16; and an interface layer, formed between the light reflection layer 18 and the WORM-type recording layer 14. The label layer may be composed of an ultraviolet curing resin, a thermosetting resin, a heat-drying resin, or the like.
The above essential layers and additional layers may have a single- or multi-layer structure.
In the optical information recording medium 10A of Embodiment (1), it is preferred that the light reflection layer 18 is formed between the substrate 12 and the WORM-type recording layer 14 to increase the reflectance to the laser light 46 and to improve the recording/reproducing properties.
For example, the light reflection layer 18 can be formed on the substrate 12 by vacuum-depositing, sputtering, or ion-plating a light reflective substance having a high reflectance to the laser light 46.
The thickness of the light reflection layer 18 is generally 10 to 300 nm, preferably 30 to 200 nm.
The reflectance is preferably 70% or more.
Examples of the light reflective substances with high reflectance include metals of Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, etc., metalloids, and stainless steels. These light reflective substances may be used singly or in combination, or as an alloy. The light reflective substance is preferably Cr, Ni, Pt, Cu, Ag, Au, Al, or a stainless steel, particularly preferably Au, Ag, Al, or an alloy thereof, most preferably Au, Ag, or an alloy thereof.
As shown in
The barrier layer 20 can act to increase the storability of the WORM-type recording layer 14, increase the adhesion between the WORM-type recording layer 14 and the cover layer 16, control the reflectance, and control the heat conductivity.
The barrier layer 20 may be composed of any material that can transmit the light for recording and reproducing and can provide the above functions. In general, the material of the barrier layer 20 is preferably a dielectric substance having a low gas and water permeability.
Specific examples of the materials include nitrides, oxides, carbides, and sulfides of Zn, Si, Ti, Te, Sn, Mo, Ge, Nb, Ta, etc. The material of the barrier layer 20 is preferably MoO2, GeO2, TeO, SiO2, TiO2, ZnO, SnO2, ZnO—Ga2O3, Nb2O5, or Ta2O5, more preferably SnO2, ZnO—Ga2O3, SiO2, Nb2O5, or Ta2O5.
The barrier layer 20 can be formed by a vacuum film forming method such as vacuum deposition, DC sputtering, RF sputtering, or ion plating. The barrier layer 20 is preferably formed by a sputtering method.
The thickness of the barrier layer 20 is preferably 1 to 200 nm, more preferably 2 to 100 nm, further preferably 3 to 50 nm.
The optical information recording medium of Embodiment (2) has the substrate, the WORM-type recording layer, and the protective substrate, and is preferably a laminate type recording medium. Typical layer structures of the optical information recording medium are as follows:
The above first to fifth layer structures are considered to be illustrative, and the layer structure of the optical information recording medium is not limited thereto. A part of the first to fifth layer structures may be replaced or omitted. The WORM-type recording layer may be formed also on the protective substrate. In such a case, the resultant optical information recording medium is capable of recording and reproducing on the both surfaces. Each of the above-described layers may have a single- or multi-layer structure.
An example of the optical information recording medium of Embodiment (2), which contains a substrate, a WORM-type recording layer, a light reflection layer, an adhesion layer, and a protective substrate in this order, is described in detail below. The optical information recording medium having such a structure is shown in
In Embodiment (2), the substrate 24 has pregrooves 36 (guide grooves) with particular track pitch, groove width (half width), groove depth, and wobble amplitude to be hereinafter described. The pregrooves 36 are formed in order to achieve a recording density higher than those of CD-R and DVD-R, and are suitable for optical information recording media using bluish purple laser lights.
The track pitch of the pregrooves 36 is 200 to 600 nm. The track pitch is preferably 450 nm or less, more preferably 430 nm or less. Further, the track pitch is preferably 300 nm or more, more preferably 330 nm or more, further preferably 370 nm or more. When the track pitch is 200 nm or more, the pregrooves can be formed accurately to prevent crosstalk. When the track pitch is 600 nm or less, high-density recording can be achieved.
The groove width (the half width) of each pregroove 36 is 50 to 300 nm. The groove width is preferably 290 nm or less, more preferably 280 nm or less, further preferably 250 nm or less. Further, the groove width is preferably 100 nm or more, more preferably 120 nm or more, further preferably 140 nm or more. When the groove width of the pregroove 36 is 50 nm or more, the groove can sufficiently be transferred in a forming process, and the error rate can be reduced in a recording process. When the groove width is 300 nm or less, a pit formed in a recording process can be reduced to prevent crosstalk, and a sufficient modulation can be achieved.
The groove depth of each pregroove 36 is 30 to 150 nm. The groove depth is preferably 140 nm or less, more preferably 130 nm or less, further preferably 120 nm or less. Further, the groove depth is preferably 40 nm or more, more preferably 50 nm or more, further preferably 60 nm or more. When the groove depth of the pregroove 36 is 30 nm or more, a sufficient recording modulation can be obtained. When the groove depth is 150 nm or less, a high reflectance can be obtained.
The thickness of the substrate 24 is generally 0.1 to 1.0 mm, preferably 0.2 to 0.8 mm, more preferably 0.3 to 0.7 mm.
An undercoat layer may be formed on a surface of the substrate 24, on which the WORM-type recording layer 26 is formed, to improve flatness and adhesion.
Examples of materials of the undercoat layer include polymers such as polymethyl methacrylates, acrylic acid-methacrylic acid copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohols, N-methylolacrylamide, styrene-vinyltoluene copolymers, chlorosulfonated polyethylenes, nitrocelluloses, polyvinyl chlorides, chlorinated polyolefins, polyesters, polyimides, vinyl acetate-vinyl chloride copolymers, ethylene-vinyl acetate copolymers, polyethylenes, polypropylenes, and polycarbonates, and surface modifying agents such as silane coupling agents.
The undercoat layer may be formed by dissolving or dispersing the material in an appropriate solvent, and by applying thus-obtained coating liquid to the substrate by a coating method such as spin coating, dip coating, or extrusion coating.
The thickness of the undercoat layer is generally 0.005 to 20 μm, preferably 0.01 to 10 μm.
The details of the WORM-type recording layer 26 used in Embodiment (2) are the same as those of the WORM-type recording layer 14 used in Embodiment (1).
In Embodiment (2), the light reflection layer 30 may be formed on the WORM-type recording layer 26 to increase the reflectance to the laser light 46 and to improve the recording/reproducing properties. The details of the light reflection layer 30 used in Embodiment (2) are the same as those of the light reflection layer 18 used in Embodiment (1).
In Embodiment (2), the adhesion layer 32 may be formed between the light reflection layer 30 and the protective substrate 28 to increase the adhesion between the light reflection layer 30 and the protective substrate 28.
The adhesion layer 32 is preferably composed of a light curing resin. It is preferred that the light curing resin has a small cure shrinkage ratio from the viewpoint of preventing curling of the resultant disk. Examples of such light curing resins include UV curing resins (UV curing adhesives) such as SD-640 and SD-661 available from Dainippon Ink and Chemicals, Inc.
The adhesion layer 32 preferably has a thickness of 1 to 1000 μm to maintain elasticity.
The material and shape of the protective substrate 28 (a dummy substrate) used in Embodiment (2) may be the same as those of the substrate 24. The thickness of the protective substrate 28 is generally 0.1 to 1.0 mm, preferably 0.2 to 0.8 mm, more preferably 0.3 to 0.7 mm.
In the optical information recording medium 10B of Embodiment (2), a protective layer may be formed to physically and chemically protect the light reflection layer 30, the WORM-type recording layer 26, etc.
Examples of materials of the protective layer include inorganic substances such as ZnS, ZnS—SiO2, SiO, SiO2, MgF2, SnO2, and Si3N4, and organic substances such as thermoplastic resins, thermosetting resins, and UV curing resins.
For example, a plastic material may be extruded into a film and stuck on the light reflection layer by an adhesive to form the protective layer. The protective layer may be formed by vacuum deposition, sputtering, coating, or the like.
In the case of using a thermoplastic or thermosetting resin for the protective layer, the protective layer may be formed by dissolving the resin in an appropriate solvent and by applying and drying thus-obtained coating liquid. In the case of using a UV curing resin for the protective layer, the protective layer may be formed by applying the resin or a coating liquid containing the resin and an appropriate solvent, and by irradiating the applied resin with a UV light to harden the resin. Various additives such as antistatic agents, antioxidants, and UV absorbers may be added to these coating liquids in accordance with the purpose.
The protective layer generally has a thickness of 0.1 μM to 1 mm.
The optical information recording medium 10B of Embodiment (2) may have another layer in addition to the above layers as far as it does not interfere with the advantageous effects of the present invention. The details of such layers in Embodiment (2) are the same as those in Embodiment (1).
The present invention further relates to a method for recording information on the optical information recording medium having a substrate and a recording layer. In the information recording method of the present invention, the optical information recording medium of the present invention is irradiated with a laser light, to record information on the recording layer containing the azo-metal complex dye derived from a metal ion or a metal oxide ion and an azo dye represented by the general formula (1-1) or (1-2).
For example, information may be recorded on the above optical information recording media 10A and 10B according to Embodiments (1) and (2) in the following manner.
First the substrate side or the protective layer side of the optical information recording medium is irradiated with a recording light such as a semiconductor laser light while rotating the optical information recording medium at a constant linear speed (e.g. 0.5 to 10 m/second) or a constant angular speed. With the recording light, the optical properties of the recording medium are changed and the information is recorded in portions irradiated with the light. In the embodiment shown in
In the present invention, it is preferred that the information is recorded by irradiation with a laser light 46 having a wavelength of 440 nm or less. The recording light is preferably a semiconductor laser light having an emission wavelength of 440 nm or less, further preferably a bluish purple semiconductor laser light having an emission wavelength of 390 to 415 nm, or a bluish purple SHG laser light having a center emission wavelength 425 nm obtained by treating a semiconductor infrared laser light having a center emission wavelength of 850 nm with an optical waveguide device. Further, it is preferred from the viewpoint of the recording density that the recording light is a bluish purple semiconductor laser light having an emission wavelength of 390 to 415 nm. The recorded information may be reproduced by irradiating the substrate side or the protective layer side of the optical information recording medium with a semiconductor laser light and by detecting the reflected light while rotating the recording medium at the above constant linear speed.
Then, a method for synthesizing the azo-metal complex dye of the present invention is described below.
Examples of methods for synthesizing the azo dye represented by the general formula (1-1) or (1-2) include those described in Japanese Laid-Open Patent Publication Nos. 61-36362 and 2006-57076. The synthesis is not limited thereto, and the azo dye may be synthesized by using another reaction solvent, or acid, and may be synthesized by a coupling reaction under the presence of a base such as sodium acetate, pyridine, or sodium hydroxide. Typical examples of the method for synthesizing the azo dye are hereinafter described in detail in following Examples using a compound (A-3).
Examples of methods for synthesizing the azo-metal complex dye by a reaction between the azo dye and the metal ion include methods of stirring the azo dye and a metal salt (which may be a metal complex or a metal oxide salt) under the presence of a base in an organic solvent, water, or a mixture thereof. There are no particular restrictions on the type of the metal salt, the type of the base, the type of the organic solvent or the mixture thereof, and the reaction temperature. Typical examples of the method for synthesizing the azo-metal complex dye are hereinafter described in detail in Examples, taking a compound (M-1) for instance.
In a synthesis method, a salt of Co, Ni, Fe, Cu, Zn, etc. is reacted with the azo dye represented by the general formula (1-1) or (1-2) in the presence of the base, whereby the azo-metal complex dye represented by the general formula (2-1) or (3-1) can be obtained. In a case where the base is not used in the synthesis system, a neutral or cationic azo-metal complex can be obtained.
The present invention is described in more detail below with reference to Examples without intention of restricting the scope of the invention.
Synthesis of the azo dye represented by the general formula (1-1) or (1-2) is described below without intention of restriction.
2 g of a compound (1), 2.6 ml of acetic acid and 4 ml of propionic acid were added to a 100-ml conical flask, and 3.7 ml of a hydrochloric acid (35 to 37%) was added thereto dropwise under ice cooling. The mixture was cooled to 0° C. to 5° C. in an ice bath, and 2 ml of an aqueous solution containing 0.92 g of NaNO2, which was cooled to 5° C. or lower beforehand, was slowly added thereto dropwise. The resultant mixture was stirred at 0° C. to 5° C. for 15 minutes. Then, 40 ml of a methanol solution containing 2.2 g of a compound (2) was kept at 0° C. to 5° C. under ice cooling, and the above obtained acidic solution was added thereto and stirred for 1 hour. The resultant solution was heated to the room temperature, stirred for 2 hours, and subjected to filtration to isolate the precipitates. The precipitates were washed with a small amount of methanol, and purified by a silica gel column chromatography using an eluent of ethyl acetate, to obtain 0.8 g of a compound (A-3).
The obtained compound was identified by 300 MHz 1H-NMR.
1H-NMR (DMSO-d6) [ppm]; 13.70 (1H, br), 13.5 (1H, s), 2.46 (3H, s), 1.51 (9H, s), 1.44 (9H, s)
1 g of a compound (5) and 13 ml of a 85% aqueous phosphoric acid solution were added to a 100-ml three-necked flask, and cooled to 0° C. to 5° C. while stirring. 0.53 g of sodium nitrite was added thereto and stirred at 0° C. to 5° C. for 30 minutes. Thus-obtained acidic solution was slowly added dropwise to 20 ml of a methanol solution containing 1.44 g of a compound (6) cooled at 5° C. or lower, and stirred for 1 hour. The resultant solution was heated to the room temperature, stirred for 2 hours, and the generated precipitates were isolated by filtration to obtain 2.0 g of a compound (A-1). The obtained compound was identified by 300 MHz 1H-NMR.
1H-NMR (CDCl3) [ppm]; TM3.21 (m), 1.55 (s), 1.49 (s), 1.42 (s)
Compounds (A-7), (A-9), (A-16), and (A-21) were synthesized in the same manner as the compound (A-3). Various azo dyes of the present invention can be synthesized by the same method. The obtained compounds were identified by 300 MHz 1H-NMR. The obtained NMR spectrum data is shown below.
(A-7): 1H-NMR (DMSO-d6) [ppm]; TM13.95 (2H, br), 2.47 (3H, s), 1.52 (9H, s)
(A-9): 1H-NMR (DMSO-d6) [ppm]; TM13.45 (2H, br), 10.06 (1H, s), 7.85 (2H, d), 7.52 (1H, t), 7.37 (1H, d), 7.24 (1H, t), 6.82 (2H, d), 3.77 (6H, s), 3.07 (3H, s), 1.44 (9H, s)
Synthesis of the azo-metal complex dye represented by the general formula (2-1) or (3-1) is described below without intention of restricting the scope of the invention.
1 g of a compound (A-3) and 20 ml of methanol were added to a 50-ml eggplant-shaped flask, and 2.1 ml of triethylamine was added thereto dropwise while stirring. The mixture was stirred for 10 minutes, to this was added 0.7 g of Co(OAc)2.4H2O, and the resultant mixture was refluxed under heating for 1 hour. 50 ml of a distilled water was added to the mixture, and the mixture was cooled to the room temperature and subjected to filtration to isolate the precipitates. The precipitates were washed with a distilled water, and dried to obtain 0.9 g of a compound (M-1). The obtained compound was identified by MALDI-TOF-MS; m/z=762 (nega), 102 (posi).
A compound (M-2) was synthesized in the same manner as the compound (M-1) except for using Ni(OAc)2.4H2O instead of Co(OAc)2.4H2O. The obtained compound was identified by MALDI-TOF-MS; m/z=762 (nega), 102 (posi).
A compound (M-13) was synthesized in the same manner as the compound (M-1) except for using Cu(OAc)2H2O instead of Co(OAc)2.4H2O. The obtained compound was identified by MALDI-TOF-MS; m/z=893 (nega), 829 (nega), 102 (posi), where compounds having 2 or 3 Cu ions with 2 azo dye ligands were detected in the negative mode.
The obtained compound (M-13) was further identified by ESI-MS. ESI-MS measurement was carried out using an HPLC (TSK GEL ODS-80Ts, 2.0×150 mm, eluent 10-mM ammonium acetate methanol/water solution). Results of ESI-MS measurement of the compound (M-13); m/z=1725 (nega), 891 (nega), 862 (nega), 830 (nega), 415 (posi).
The difference between the results of MALDI-TOF-MS and ESI-MS seems to depend on the intensity difference of isotope peaks detected in ionization or on the solution used (mainly on whether ammonium acetate is used or not).
It was confirmed from the results that the ratios of the metal ion/the azo dye ligand were 5/4, 3/2, and 2/2 in the solution.
Further, the obtained compound (M-13) was subjected to an ESR analysis, whereby it was found that the compound (M-13) had a structure with a ratio of Cu ion/azo dye anion of 1/1 in the powder state. Though the structure of the compound (M-13) in the solution state (in tetrahydrofuran, 10 K) was different from the structure in the solid state, the structure in the solution state could not be determined by the ESR analysis.
Compounds (M-22), (M-26), (M-32), and (M-40) were synthesized in the same manner as the compounds (M-1), (M-2), and (M-13).
Various azo-metal complex dyes of the present invention can be synthesized by the same synthesis method. The compounds can be identified by MALDI-TOF-MS, ESI-MS, or ESR analysis.
A compound (M-41) was synthesized in the same manner as the compound (M-13) except for using a compound (A-1) instead of the compound (A-3).
The azo-metal complex dyes obtained in the same manner as the compound (M-1) can undergo a cation exchange reaction in a solvent. An example of the cation exchange reaction is shown below.
300 mg of the compound (M-1) and 10 ml of methanol were added to a 50-ml eggplant-shaped flask, and to this were added a solution prepared by dissolving 200 mg of a compound (3) in 5 ml of methanol and 5 ml of a distilled water while stirring. The mixture was refluxed under heating for 1 hour. Then, to the mixture was added 20 ml of a distilled water, the resultant mixture was cooled to the room temperature, and the precipitates were isolated by filtration. The precipitates were washed with a distilled water, and dried to obtain 270 mg of a compound (M-6). The obtained compound was identified by MALDI-TOF-MS; m/z=762 (nega), 297 (posi).
The compounds (M-14), (M-17), (M-23), and (M-36) were synthesized in the same manner as the compound (M-6). Various azo-metal complex dyes having various cations according to the present invention can be synthesized by the same method. The compounds can be identified by MALDI-TOF-MS.
A polycarbonate resin substrate having a thickness of 1.1 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, which had spiral pregrooves 34 with a track pitch of 320 nm, a groove width (a concave portion width) of 190 nm, a groove depth of 47 nm, a groove inclination angle of 65°, and a wobble amplitude of 20 nm, was prepared by injection forming. Mastering of a stamper used in the injection forming was carried out by using a laser cutting (351 nm).
A 60-nm-thick, ANC light reflection layer (containing 98.1 at % of Ag, 0.7 at % of Nd, and 0.9 at % of Cu) was formed as a vacuum-formed film on the substrate 12 by DC sputtering using CUBE manufactured by Unaxis in an Ar atmosphere. The thickness of the light reflection layer 18 was controlled by selecting the sputtering time.
Dye-containing coating liquids of Examples 1 to 10 were prepared by dissolving 1 g of each of the compounds (M-1), (M-13), (M-14), (M-17), (M-22), (M-23), (M-26), (M-32), (M-36), and (M-40) in 100 ml of 2,2,3,3-tetrafluoropropanol. Then, each of the prepared dye-containing coating liquids was applied to the first light reflection layer 18 by a spin coating method under conditions of 23° C. and 50% RH while changing the rotation rate within a range of 500 to 2,200 rpm, to form a WORM-type recording layers 14.
The formed WORM-type recording layer 14 was subjected to an annealing treatment in a clean oven. In the annealing treatment, the substrate 12 was supported at 80° C. for 1 hour by a vertical stack pole with a distance kept by a spacer.
A 10-nm-thick, barrier layer 20 of Nb2O5 was formed on the WORM-type recording layer 14 by DC sputtering using CUBE manufactured by Unaxis in an Ar atmosphere.
A polycarbonate film (PUREACE available from Teijin, 80-μm thick) having an inner diameter of 15 mm and an outer diameter of 120 mm was used as a cover layer 16. A sticking layer having a glass-transition temperature of −26° C. was disposed on one side of the polycarbonate film such that the total thickness of the sticking layer and the polycarbonate film was 100 μm.
The cover layer 16 was placed on the barrier layer 20 such that the barrier layer 20 faced the sticking layer. Then, the cover layer 16 was pressed by a pressing member, to stick the cover layer 16 on the barrier layer 20. An optical information recording medium 10A having the layer structure shown in
Optical information recording media of Examples 1 to 10 were produced in this manner respectively.
Optical information recording media of Comparative Examples 1 to 4 were produced in the same manner as Example 1 except for using comparative compounds (A) to (D) instead of the compound (M-1) in the WORM-type recording layer 14.
For example, in Comparative Example 1, 1 g of the following comparative compound (A) was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a dye-containing coating liquid. Except for this, the optical information recording medium of Comparative Example 1 was produced in the same manner as Examples 1 to 10. Also the optical information recording media of Comparative Examples 2 to 4 were produced in the same manner as Comparative Example 1 except for using 1 g of the following comparative compounds (B) to (D).
Comparative compound (A), described in Japanese Laid-Open Patent Publication No. 2001-158862
Comparative compound (B), described in Japanese Laid-Open Patent Publication No. 2001-158862
Comparative compound (C), described in Japanese Laid-Open Patent Publication No. 2001-306070
Comparative compound (D), described in Japanese Laid-Open Patent Publication No. 2005-297406
A 0.16-μm signal (2T) was recorded and reproduced in each of the produced optical information recording media by using a recording/reproducing evaluator (DDU1000 manufactured by Pulstec Industrial Co., Ltd.) having 403-nm laser and NA 0.85 pickup under conditions of a clock frequency of 66 MHz and a linear speed of 4.92 m/s. The recorded pit was reproduced by a spectrum analyzer (FSP-3 manufactured by Rohde & Schwarz). An output at 16 MHz after recording was used as Carrier output, an output at 16 MHz before recording was used as Noise output, and a C/N value was obtained by the output after recording—the output before recording. In this evaluation, the signal was recorded on the grooves by the optical information recording method of the present invention. Further, the recording power was 5 mW, and the reproducing power was 0.3 mW. The results are shown in Table 3. The 2T recording C/N ratio is used as a measure of recording properties. As the recording power is increased, the 2T recording C/N ratio is increased. In view of both the 2T recording C/N ratio and the recording sensitivity, when the C/N ratio (after recording) is 35 dB or more at approximately 5 mW, the recording medium has sufficient recording sensitivity and reproduced signal intensity, and thereby has satisfactory recording properties.
The dye-containing coating liquids of Examples 1 to 10 and Comparative Examples 1 to 4 were prepared, and each coating liquid was applied to a 1.1-mm-thick glass plate by a spin coating method under conditions of 23° C. and 50% RH while changing the rotation rate within a range of 500 to 1,000 rpm. The glass plate with the dye film was stored for 24 hours under conditions of 23° C. and 50% RH, and then subjected to a light fastness test using a merry-go-round-type light fastness tester (Cell Tester Model III manufactured by Eagle Engineering, equipped with WG320 Filter manufactured by Schott). The absorption spectrum of the dye film was measured using UV-1600PC manufactured by SHIMADZU immediately before the light fastness test and 48 hours after the light fastness test, and the change of the absorbancy at the maximum absorption wavelength was evaluated.
(1)Evaluated as “Excellent” when the residual dye ratio was 90% or more at absorption λmax 48 hours after the irradiation with the Xe light, evaluated as “Good” when the ratio was 85% or more and less than 90%, evaluated as “Fair” when the ratio was 75% or more and less than 85%, and evaluated as “Poor” when the ratio was less than 75%;
(2)Evaluated as “Excellent” when the 2T recording C/N was 39 dB or more, evaluated as “Good” when the ratio was 35 dB or more and less than 39 dB, evaluated as “Fair” when the ratio was 30 dB or more and less than 35 dB, and evaluated as “Poor” when the ratio was less than 30 dB; and
(3)Measurement or recording could not carried out because the recording layer could not sufficiently formed due to poor solubility.
As shown in Table 3, the azo-metal complex dyes used in Examples 1 to 10 were more excellent in light fastness and recording/reproducing properties as compared with the conventional azo-metal complexes used in Comparative Examples 1 to 4. Further, the optical information recording media of the invention were capable of recording and reproducing even after the irradiation with a Xe light for 55 hours, and thus were excellent in light fastness.
Furthermore, the azo-metal complex dyes of Examples according to the present invention had excellent solubility in the coating solvent, and had excellent stability in film.
Each of the azo-metal complex dyes of Examples according to the present invention was dissolved in 2,2,3,3-tetrafluoropropanol such that the absorbancy was 0.95 to 1.05 (cell width of 1 cm). The light fastness of thus-obtained solution was evaluated in the same manner as the above dye films. As a result, all the solutions were remarkably excellent in light fastness, and had a residual dye ratio of 90% or more after 48 hours. The light fastness is an important property required for various applications. The azo-metal complex dye of the present invention shows excellent light fastness in film and solution, and thereby can show excellent functions in various applications of inks, color filters, color conversion filters, photographic materials, thermal transfer recording materials, and the like.
Further, the azo-metal complex dyes of Examples were not decomposed in the powder state and film state even at 150° C. or higher. Thus, it is clear that the azo-metal complex dye of the present invention is excellent in thermal stability. The azo-metal complex dye of the present invention can show excellent functions in various applications of inks, color filters, color conversion filters, photographic materials, and the like.
It should be noted that the optical information recording medium and the azo-metal complex dye of the present invention are not limited to the above embodiments, and various changes and modifications may be made therein without departing from the scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-265692 | Sep 2006 | JP | national |
| 2007-106441 | Apr 2007 | JP | national |
| 2007-106459 | Apr 2007 | JP | national |
