JP2510529B2 - Optical information recording medium - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an optical information recording medium suitable for optical writing and recording by a laser or the like, and more particularly, an improved optical recording which can be used for an optical disc, an optical card and the like. It concerns media.

[Conventional technology]

In general, an optical disc or an optical card has a small, optically detectable size, for example, about 1 μpit formed in a thin recording layer provided on a substrate, and is formed into a spiral or circular or linear track form with high density. Information can be stored. In order to write information on such a disk or card, a laser focused on the surface of the laser sensitive layer is scanned, and only the surface irradiated with this laser beam forms a pit,
The pit is formed in the form of a spiral or circular or linear track. The laser sensitive layer can absorb laser energy to form an optically detectable pit. For example, in the heat mode recording system, the laser-sensitive layer absorbs thermal energy, and a small recess (pit) can be formed at that portion by evaporation or melting. Further, in another heat mode recording method, a pit having an optically detectable density difference can be formed at the position by absorbing the irradiated laser energy.

The information recorded on this optical disc and optical card is
It is detected by scanning the laser beam along the track and reading the optical change of the part where the pit is formed and the part where the pit is not formed. For example, in the case of an optical disk or optical card, laser light is scanned along the track,
The energy reflected by the disk or card is monitored by the photo detector. In the portion where the pits are formed, the laser light is sufficiently reflected and the output of the photodetector becomes large. On the other hand, in the portion where the pit is not formed, the reflection is low and the output of the photodetector is small.

Optical information recording media used for such optical discs and optical cards have mainly been made of inorganic materials such as aluminum, metal thin films such as gold vapor deposition films, bismuth thin films, tellurium oxide thin films and chalcogenite amorphous glass films. The one used is proposed. These thin films have disadvantages such as poor storage stability, low resolution, low recording density, and high cost. Recently, it has been proposed to use an organic dye thin film, whose physical properties can be changed by light of a relatively long wavelength, for the recording layer. Although this organic dye thin film eliminates the above-mentioned drawbacks, organic dyes having absorption characteristics on the long wavelength side generally have problems such as low stability to heat and light. In consideration of these points, the organic dye used for the recording material is required to have the following properties. That is, 1. It is not toxic. 2. It has absorption near 800 nm and has a large absorption coefficient. 3. It has good solubility in organic solvents. 4. It has a large reflectance near 800 nm in a thin film state. Difficult to crystallize 6. Stable to ultraviolet and visible light 7. Stable to heat 8. Stable to humidity 9. Easy to synthesize As a dye satisfying these performances to some extent , A dye represented by the general formula (1) has been proposed (JP-A-58-219090).

The advantages of such organic dyes as compared with the conventionally used inorganic compounds are that they are not toxic in 1. and good in solubility in 3. On the other hand, they have sufficient reflectance but crystallize in a thin film state. There is a problem that it is easy to change.

The reflectance is necessary for the laser to scan the track accurately when monitored by a photodetector, but when crystallization occurs, the absorption rate of the organic film,
The reflectance is significantly reduced and it becomes difficult to form pits, making it impossible to record.

[Problems to be solved by the invention]

The present invention has been made in view of the above circumstances, and a main object thereof is to provide an optical information recording medium containing a polymethine dye and having high reflectance and good storage stability.

[Means for solving problems]

 The dye used in the present invention is represented by the general formula (1).

 R₁, R₂, R₃, R_FourAnd R_FiveIs a hydrogen atom or an alkyl group
(For example, methyl group, ethyl group, n-propyl group, iso
-Propyl group, n-butyl group, sec-butyl group, iso-butyl
Chill group, t-butyl group, n-amyl group, t-amyl group,
n-hexyl group, n-octyl group, t-octyl group
And other alkyl groups such as substituted alkyl groups.
Group (eg, 2-hydroxyethyl group, 3-hydroxy group)
Cypropyl group, 4-hydroxybutyl group, 2-acetoxy group
Ciethyl group, carboxymethyl group, 2-carboxyethyl
Group, 3-carboxypropyl group, 2-sulfoethyl
Group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfate propyl group, 4-sulfate butyl group,
N- (methylsulfonyl) -carbamylmethyl group, 3-
(Acetylsulfamyl) propyl group, 4- (acetyl
Sulfamyl) butyl group, etc.), cyclic alkyl group (eg.
For example, cyclohexyl group, etc.), alkenyl group (vinyl
Group, allyl group, propenyl group, butenyl group, pentenyl group
Group, hexenyl group, heptenyl group, octenyl group, dode
Cinyl group, prenyl group, etc.), aralkyl group (eg,
Benzyl group, phenethyl group, α-naphthylmethyl group, β
-Naphthylmethyl group, etc., substituted aralkyl group (eg.
For example, carboxybenzyl group, sulfobenzyl group, hydro
Xybenzyl group, etc.). Furthermore, R₁, R₂, R₃, R
_FourAnd R_FiveIs a substituted or unsubstituted aryl group (eg
For example, phenyl group, naphthyl group, tolyl group, xylyl group,
Methoxyphenyl group, dimethoxyphenyl group, trimetho
Xyphenyl group, ethoxyphenyl group, dimethylamino
Phenyl group, diethylaminophenyl group, dipropyl group
Minophenyl group, dibenzylaminophenyl group, diphenyl
Nylaminophenyl, etc.), substituted or unsubstituted
Tricyclic groups (eg pyridyl group, quinolyl group, lepidyl group
Group, methylpyridyl group, furyl group, thienyl group, India
Ryryl group, pyrrole group, carbazolyl group, N-ethylcarbyl
Bazolyl group) or substituted or unsubstituted styryl group
(For example, styryl group, methoxystyryl group, dimethoxy group
Cystyryl group, trimethoxystyryl group, ethoxystyryl
Ryl group, dimethylaminostyryl group, diethylaminos
Tyryl group, dipropylaminostyryl group, dibenzyl group
Minostyryl group, diphenylaminostyryl group, 2,2-
Diphenyl vinyl group, 2-phenyl-2-methyl vinyl
Group, 2- (dimethylaminophenyl) -2-phenylbi
Nyl group, 2- (diethylaminophenyl) -2-phenyl
Ruvinyl group, 2- (dibenzylaminophenyl) -2-
Phenyl vinyl group, 2,2-di (diethylaminophenyl)
Vinyl group, 2,2-di (methoxyphenyl) vinyl
Group, 2,2-di (ethoxyphenyl) vinyl group, 2- (di
Methylaminophenyl) -2-methylvinyl group, 2-
(Diethylaminophenyl) -2-ethylvinyl group
Indicate). m is 0 or 1 and n is 0, 1 or 2
Is. X Is chloride ion, bromide ion, iodide
Product ion, perchlorate ion, benzene sulfonate
ON, P-toluenesulfonate ion, methyl sulfate
Ion, ethyl sulfate ion, propyl sulfate ion,
Tetrafluoroborate ion, tetraphenyl borate
Salt ion, hexafluorophosphate ion, benzene
Rufate ion, acetate ion, trifluoroacetic acid
Salt ion, propion acetate ion, benzoate ion
Ion, oxalate ion, succinate ion, malonate
Ion, oleate ion, stearate ion,
Citrate ion, monohydrogen diphosphate ion, dihydrogen mono
Phosphate ion, pentachlorostannate ion, chloro
Sulfonate ion, fluorosulfonate ion,
Lifluoromethanesulfonate ion, hexafluoro
Antimonate ion, molybdate ion, tongue
Stenate ion, titanate ion, zirconate ion
Represents anions such as on.

Such a dye generally has an absorption peak with a large absorption coefficient near 800 nm, has good solubility in an organic solvent, has light resistance, and is an excellent optical information recording medium. Moreover, it has a sufficient reflectance, but tends to crystallize over time. The present invention provides a medium having improved reflectance and excellent storage stability by including a metal chelate compound in these polymethine dyes.

The behavior of these metal chelate compounds in the recording layer is not clear, but it affects the stacking interaction between dyes, changes the packing state, and increases the refractive index in the recording layer, causing reflection in the thin film state. It is thought that the rate has improved. In addition, it is considered that such a state of association between the dye and the chelate compound prevented crystallization and increased storage stability.

Next, typical examples of the polymethine compound represented by the general formula (1) will be given.

These polymethine compounds are described by Bernard S. Wildi et al.
J.Am.Chem.Soc (Journal of American Chemical Society) 80 3772-3777 (1958) and H.Schmidt et al. Ann (Liewitz Anna Rendel Chemie) 623 2
04 to 216 or R. Wlzinger et al., Heln. Chim. Acta (Herpetica / Simika / Acta) 24 369, etc. and can be easily obtained by synthesizing according to the synthetic method.

The chelate compound used in the present invention has a central metal of Zn, C
Transition metals such as u, Ni, Co, Mn, Pd and Zr are preferable. Specific examples of the chelate compound that can be used as a stabilizer as described above are shown below.

1) Thiosalicylaldoxime represented by the following formula R ₁₁ may be a hydrogen atom, a hydroxyl group, an alkyl group, or an aryl group, and may be bonded to the other R ₁₁ . R ₁₂ represents an alkyl group, a halogen atom, a hydrogen atom, a nitro group or a benzo-condensed group, and the central metal M represents Cu, Ni, Co or Pd.

2) Thioacetothiophenone type R ₂₁ represents an alkyl group, an aryl group, R ₂₂ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group or a benzo-condensed system, and M represents Cu, Ni or Pd.

3) Acetothiophenone type R ₃₁ represents an alkyl group, an aryl group, R ₃₂ represents a hydrogen atom, a halogen atom, an alkyl group or a benzo-condensed group, and M represents
Represents Cu, Ni, or Pd.

4) Oxyxanthione type R ₄₁ represents a hydrogen atom, a halogen atom or an alkyl group, and M represents Cu or Ni.

Concrete example. No. R ₄₁ M M-4-1 H Cu M-4-2 H Ni M-4-3 4-CH ₃ Ni 5) Pyromeconic acid type R ₅₁ represents a hydrogen atom or an alkyl group, M is Cu, N
represents i, Co or Mn.

Concrete example. No. R ₅₁ M M-5-1 H Mn M-5-2 H Ni M-5-3 2-C ₂ H ₅ Ni 6) Mercaptobenzazole type R ₆₁ is a sulfur atom, a substituted or unsubstituted amino group, an oxygen atom or a thioketone group, R ₆₂ is a hydrogen atom, an alkyl group,
Represents a halogen atom or amino group, M is Zn, Cu or Ni
Represents

7) Hydroxamic acid type R ₇₁ represents an alkyl group, an aryl group or a styryl group, and M represents Cu, Ni or Co.

No. R ₇₁ M M-7-1 C ₃ H ₇ Cu M-7-2 C ₆ H ₅ Ni M-7-3 C ₆ H ₅ CH = CH-Ni M-7-4 Cl-C ₆ H ₄ CH = CH-Ni 8) Biscyclopentadiene system R ₈₁ represents a hydrogen atom, a halogen atom, an alkyl group, an acyl group or an aryl group, and M represents Ni or Zr.

9) Nitrosohydroxylamine type R ₉₁ represents an alkyl group or an aryl group, and M represents Cu, Ni or Co.

No. R ₉₁ MM-9-1 C ₃ H ₇ Cu M-9-2 C ₃ H ₇ Ni M-9-3 p- (CH ₃ ) ₂ N-C ₆ H ₄ -Cu M-9-4 _{p- (CH 3) 2 N-} C 6 H 4 - Ni 10) dioxime type R ₁₀₁ and R ₁₀₂ represent an alkyl group or an aryl group, and M represents Ni.

11) Compound represented by the following formula R ₁₁₁ and R ₁₁₂ are a hydrogen atom, a halogen atom or an alkyl group, X is an oxygen atom or a sulfur atom, and M is Ni.

12) Compound represented by the following formulaR₁₂₁, R₁₂₂Is a hydrogen atom, an alkyl group, a halogen atom or
Nitro group, X is oxygen atom or sulfur atom, M is Ni, Y Is
Represents a quaternary ammonium cation.

13) Anthranilic acid type R ₁₃₁ is a hydrogen atom, a halogen atom, an alkyl group, an acyl group, a nitro group or an alkoxyl group, and M is Zn, Cu, Ni or
Represents Co.

No. R ₁₃₁ M M-13-1 H Cu M-13-2 4-Cl Ni M-13-3 4-NO ₂ Ni M-13-4 5-CH ₃ Ni By combining them, the reflectance can be increased, the storage stability can be improved, and a high C / N value can be obtained. Such metal chelate compound is contained in an amount of about 1 to 60% by weight based on the total amount of the recording material.

Further, a binder may be mixed in addition to the dye and the metal chelate compound. Suitable binders can be selected from a wide range of resins. Specifically, nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate / propionate, cellulose esters such as cellulose acetate / butyrate, methyl cellulose, Cellulose ethers such as ethyl cellulose, propyl cellulose, butyl cellulose, etc., vinyl resins such as polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinyl pyrrolidone, styrene-butadiene copolymer, styrene-acrylonitrile copolymer. , Styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, etc. Acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile, polyesters such as polyethylene terephthalate, poly (4,4'-isopropylidene, diphenylene) -Co-1,4-cyclohexylene dimethylene carbonate), poly (ethylenedioxy-3,3'-phenylene thiocarbonate), poly) 4,4'-isopropylidene diphenylene carbonate-co-terephthalate), Poly (4,4'-isopropylidene diphenylene carbonate), poly (4,4'-sec-butylidene diphenylene carbonate), poly (4,4'-isopropylidene diphenylene carbonate-block-oxyethylene) Polyarylate resin such as , Or polyamides,
Polyimides, epoxy resins, phenol resins, polyolefins such as polyethylene, polypropylene and chlorinated polyethylene can be used.

The organic solvent that can be used at the time of coating varies depending on whether it is in a dispersed state or an amorphous state, but in general, alcohols such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketones, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, methyl acetate, ethyl acetate, and butyl acetate Esters such as chloroform,
Aliphatic halogenated hydrocarbons such as methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene, or aromatics such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, and anisole can be used.

The coating can be carried out using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a Meyer bar coating method, a blade coating method, a roller coating method or a curtain coating method.

As the substrate, glass, polyamide, polyester,
Polyolefin, polycarbonate, epoxy, polyimide, polymethylmethacrylate, etc. are used. A groove is usually provided on the substrate for tracking, and an undercoat layer may be further provided on the substrate for improving adhesion to the recording layer or solvent resistance.

According to the present invention, it is possible to obtain an optical information recording medium having high reflectance and stable tracking, high C / N ratio, and good storage stability.

 Hereinafter, examples of the present invention will be described in detail.

〔Example〕

SiO on an acrylic disk substrate with a diameter of 130 mm and an inner diameter of 15 mm
After forming an undercoat layer (100 to 200Å) consisting of _2, a recording layer having a film thickness of 800 to 1000Å was formed by using a material containing a combination of a dye and a metal chelate compound shown in Table 1 below in a predetermined solvent.

Using a semiconductor laser beam of 830 nm from the substrate side of the recording medium thus obtained, a recording frequency of 2 MHz, a rotation speed of 1800 rp
m, recording power 8mW, read power 0.6mW, write,
The readout was performed, and the C / N value of the readout waveform was measured by spectrum analysis.

Next, the same recording medium was left for 1000 hours under the conditions of 60 ° C. and 90% RH to perform a storage stability acceleration experiment, and the reflectance C / N value was measured. The results are shown in Table 2.

[Effects of the Invention] As described above, according to the present invention, it is possible to provide an optical information recording medium in which the reflectance of a recording film is increased and the storage stability is improved by using a polymethine dye and a metal chelate compound. It is possible.

Front page continuation (72) Inventor Yoshio Takasu 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-56-55289 (JP, A) JP-A-56-109357 ( JP, A) JP 58-219090 (JP, A) JP 60-73891 (JP, A)

Claims (1)

(57) [Claims] 1. A polymethine compound represented by the following general formula (1):
In an optical information recording medium having a recording layer containing a dye
And metal chelation represented by the following general formulas (I) to (XIII)
At least one metal chelate compound selected from compounds
Is contained in the recording layer.
Information recording medium.R in formula (1)₁, R₂, R₃, R_FourAnd R_FiveAre hydrogen and al
Kill group, substituted alkyl, cyclic alkyl, alkenyl, a
Aralkyl, substituted aralkyl, aryl, substituted aryl,
Means styryl, substituted styryl, heterocycle or substituted heterocycle
Where m is 0 or 1, n is 0, 1 or 2 and X Is anion
Means a group. (I) Thiosalicylaldoxime systemR₁₁Is a hydrogen atom, hydroxyl group, alkyl group, aryl
R is the other R₁₁May be combined. R₁₂Is alkyl
Group, halogen atom, hydrogen atom, nitro group or benzo condensation
Represents a system group, and the central metal M represents Cu, Ni, Co or Pd.
You. (II) Thioacetothiophenone seriesR_{twenty one}Is an alkyl group, an aryl group, R_{twenty two}Is hydrogen atom, halogen
Atom, alkyl group, aryl group, nitro group or benzo
Represents a condensed system, and M represents Cu, Ni or Pd. (III) Acetothiophenone seriesR₃₁Is an alkyl group, an aryl group, R₃₂Is hydrogen atom, halogen
Represents a hydrogen atom, an alkyl group or a benzo-condensed group, and M is
Represents Cu, Ni or Pd. (IV) Oxyxanthione typeR₄₁Represents a hydrogen atom, a halogen atom or an alkyl group
However, M represents Cu or Ni. (V) Pyromeconic acid typeR₅₁Represents a hydrogen atom or an alkyl group, M represents Cu, N
represents i, Co or Mn. (VI) Mercaptobenzazole typeR₆₁Is a sulfur atom, a substituted or unsubstituted amino group, oxygen
Atom or thioketone group, R₆₂Is a hydrogen atom, an alkyl group,
Represents a halogen atom or amino group, M is Zn, Cu or Ni
Represents (VII) Hydroxamic acid typeR₇₁Represents an alkyl group, an aryl group or a styryl group.
However, M represents Cu, Ni or Co. (VIII) Biscyclopentadiene systemR₈₁Is hydrogen atom, halogen atom, alkyl group, acyl group
Alternatively, it represents an aryl group, and M represents Ni or Zr. (IX) Nitrosohydroxylamine typeR₉₁Is an alkyl group or an aryl group, M is Cu, Ni or Co
Represent. (X) Dioxime systemR₁₀₁, R₁₀₂Represents an alkyl group or an aryl group, M represents Ni
You. (XI) Compound represented by the following formulaR₁₁₁, R₁₁₂Is a hydrogen atom, a halogen atom or an alkyl group
X represents an oxygen atom or a sulfur atom, and M represents Ni. (XII) compound represented by the following formulaR₁₂₁, R₁₂₂Is a hydrogen atom, an alkyl group, a halogen atom or
Nitro group, X is oxygen atom or sulfur atom, M is Ni, Y Is
Represents a quaternary ammonium cation. (XIII) Anthranilic acid typeR₁₃₁Is hydrogen atom, halogen atom, alkyl group, acyl
Group, nitro group or alkoxyl group, M is Zn, Cu, Ni or
Represents Co.