JPS6374689A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To enhance the reflectance of a recording film and improve shelf stability, by containing specific polymethine dyestuff and metal chelate compound in a recording layer. CONSTITUTION:A polymethine dyestuff shown by a formula (I) and a metal chelate compound are contained in a recording layer. In the formula (I) ; R1, R2, R3, R4, and R5 represent hydrogen, alkyl, substituted alkyl, cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, arkyl, substituted arkyl, styryl, substituted styryl, heterocyclic ring or substituted heterocyclic ring, (m) represents 0 or 1, (n) represents 0, 1, or 2, and X(-) represents anion. As the metal chelate compound, a metal chelate compound of Zn, Cu, Ni, Co, Mn, Pd, or Zr is used. The polymetine dyestuff generally has an absorption peak, where an absorption factor is high, at and around 800 nm and has good solubility to an organic solvent, resistance to light, and also sufficient reflectance, but tends to crystallize with time. Therefore, the metal chelate compound is contained in the dyestuff, whereby a medium enhanced in reflectance and superior in shelf stability can be obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an optical information recording medium suitable for optical writing and recording using a laser or the like, and more specifically, an improved optical recording medium that can be used for optical disks, optical cards, etc. It is related to.

[Conventional technology]

Generally, an optical disk or an optical card is an optically detectable small optical disk formed on a thin recording layer provided on a substrate.
For example, about 1 micron pits can be arranged in the form of spiral or circular or linear tracks to store high density information. To write information to such a disk or card,
The surface of the laser sensitive layer is scanned with a focused laser beam, and only the surface irradiated with this laser beam forms pits, and these pits are formed in the form of spiral, circular, or linear tracks. The laser sensitive layer can absorb laser energy to form optically detectable pits. For example, in the heat mode recording method, the laser sensitive layer absorbs thermal energy and can form small depressions (pits) at that location by evaporation or melting. In another heat mode recording method, absorption of irradiated laser energy can form pits having an optically detectable density difference at that location.

Information recorded on the optical disc and optical card is detected by scanning a laser beam along a track and reading optical changes in areas where pits are formed and areas where pits are not formed. For example, in the case of an optical disk or an optical card, a laser beam is scanned along a track, and the energy reflected by the disk or card is monitored by a photodetector. In the area where the pits are formed, the laser beam is sufficiently reflected and the output of the photodetector becomes large. On the other hand, in areas where pits are not formed, reflection is low and the output of the photodetector is low.

Until now, inorganic materials such as metal thin films such as aluminum and gold vapor-deposited films, bismuth thin films, tellurium oxide thin films, and chalcogenide amorphous glass films have been mainly used as optical information recording media used in such optical disks and optical cards. What has been proposed has been proposed. These thin films have drawbacks such as poor storage stability, low resolution, low recording density, and high cost. Furthermore, it has recently been proposed to use an organic dye thin film whose physical properties can be changed by relatively long wavelength light in the recording layer. Although this organic dye thin film eliminates the above-mentioned drawbacks, organic dyes that generally have absorption characteristics on the long wavelength side have problems such as low stability against heat and light. Including these points, the following properties are required for organic dyes used in recording materials. That is, 1. It must be non-toxic. 2. It must have absorption near 800 nm and a large extinction coefficient. 3. It must have good solubility in organic solvents. 4. It must have a large reflectance at around 800 nm in a thin film state. 5. It must have a thin film state. Dye that satisfies these properties to some extent: 6. Stability in ultraviolet and visible light 7. Thermal stability 8. Stability against humidity 9. Easy to synthesize. As, the general formula (
The dye shown in 1) was proposed (Japanese Patent Application Laid-Open No. 58-219090
) has been done.

The advantages of organic dyes compared to conventionally used inorganic compounds are: 1. No toxicity and 3. The dissolved reflectance of
This is necessary for the laser to accurately scan the track when monitored by a photodetector, but when crystallization occurs, the absorption and reflectance of the organic film decreases significantly, making it difficult to form pits (and making recording difficult). Naru (naru)

[Problem that the invention seeks to solve]

The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical information recording medium containing a polymethine dye, which has a high reflectance and has good storage stability.

[Means for solving problems]

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

General formula (1) R1+ R2* R3+ R4 and R5 are hydrogen atoms or alkyl groups (e.g., methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 5ec
-butyl group, 1so-butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group, etc.), and further shows other alkyl groups, such as Substituted alkyl groups (e.g., 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group) , 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N-(methylsulfonyl)-carbamylmethyl group, 3-(acetylsulfamyl)propyl group, 4 -(acetylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g., cyclohexyl group, etc.), alkenyl group (vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group) , dodecynyl group, prenyl group, etc.), aralkyl group (e.g., benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl group (e.g., carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group) groups).

Further, R1, R2, R3, R4 and R5 are substituted or unsubstituted aryl groups (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group) , dimethylaminophenyl group, diethylaminophenyl group, dipropylaminophenyl group, dibenzylaminophenyl group, diphenylaminophenyl group, etc.), substituted or unsubstituted heterocyclic groups (e.g. pyridyl group, quinolyl group, revidyl group, methylbilidyl group) group, furyl group, chenyl group, indolyl group, virol group, carbazolyl group, N-ethylcarbazolyl group, etc.) or substituted or unsubstituted styryl group (e.g., styryl group, methoxystyryl group, dimethoxystyryl group, trimethoxy group) Styryl group, ethoxystyryl group, dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group, dibenzylaminostyryl group, diphenylaminostyryl group, 2,2-diphenylvinyl group, 2
-Phenyl-2-methylvinyl group, 2-(dimethylaminophenyl)-2-phenylvinyl group, 2-(diethylaminophenyl)-2-phenylvinyl group, 2-(dibenzylaminophenyl)-2-phenylvinyl group , 2.
2-di(diethylaminophenyl)vinyl group, 2.2-
di(methoxyphenyl)vinyl group, 2,2-di(ethoxyphenyl)vinyl group, 2-(dimethylaminophenyl)-2-methylvinyl group, 2-(diethylaminophenyl)-2-ethylvinyl group, etc.). m is 0 or 1, and n is 0, 1 or 2. X is chloride ion, bromide ion, iodide ion, perchlorate ion, benzenesulfonate ion, P-toluenesulfonate ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, tetra Fluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionacetate ion, benzoate ion, citrate ion , -hydrogen diphosphate ion, dihydrogen-phosphate ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, trifluoromethanesulfonate ion, hexafluoroantimonate ion,
Represents anions such as molybdate, tungstate, titanate, and zirconate.

Such dyes generally have an absorption peak with a large extinction coefficient near 800 nm, and also have good solubility in organic solvents (and light resistance, making them excellent as optical information recording media.In addition, they have good reflectance. However, the present invention provides a medium with increased reflectance and excellent storage stability by incorporating a metal chelate compound into these polymethine dyes. It is.

The behavior of these metal chelate compounds in the recording layer is not clear, but they affect the scooking interaction between dyes, change the backing state, and thicken the refractive index in the recording layer (thus creating a thin film state). It is thought that this is because the reflectance of the dye was improved.It is also thought that the association state between the dye and the chelate compound prevented crystallization and increased the storage stability.

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

D-10 θ lo4 θ IO4 l1O4 IO4 e F4 These polymethine compounds are described by Bernard S.

J, Am, Chem, Soc of W i I d i et al.
(Journal of the American Chemical Society) 803772-3777 (1958) and H. Sch.
midt et al. Ann (Richibitsch Annalendel Chemie) 623204-216 or R, W l
He ln of Z inger et al., Ch.
im.

Acta 2436
It can be easily obtained by synthesis according to the synthesis method disclosed in No. 9 and others.

The chelate compound used in the present invention has a central metal of Zn,
Transition metals such as Cu, Ni, Co, Mn, Pd, and Zr are preferred. Specific examples of chelate compounds that can be used as stabilizers as described above are listed below.

1) Thiosalicylaldoxime system R1 represented by the following formula
may be bonded to the other R1 through a hydrogen atom, hydroxyl group, alkyl group, or aryl group. R2 represents an alkyl group, a halogen atom, a hydrogen atom, a nitro group, or a benzo-fused group, and the central metal M is Cu.

Represents Ni, Co or Pd.

Specific example, No, RI R2MM-1-10H
HCu M-1-20HHN1 M-1-3H4-C2H, N1 M-1-4C2H55-CI N1M-1-51
-C3H7HC.

M-1-6n-C6H, 34-CH3N1M-1-7n
-C6H,34-CM 3PdM-1-8C6H5H
N1 M-1-9H5,6-C6H4Ni M-1-10-CH2-4-No 2Ni2) Salicylaldoxime system R1 represented by the following formula is a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, and the other R, May be combined with R2 represents a hydrogen atom, a halogen atom, an alkyl group, a nitro group, or a benzo-fused group; M is Cu;
Represents Ni, Co or Pd.

Specific example, No. RI R2M
M-2-IHHCu M-2-2CH3HN1 M-2-30H5-C2H5Cu M-2-4C2H55-C2H5N1 M-2-5C3H74-Cl N1M-2-6(
CH2) ISCH34-CH3NiM-2-7(CH2
) B CH35,6-C6H4N1M-2-8i-0
3H75,6-C6H4C.

M-2-90H4-C3H7C.

M-2-100HHPd M-2-11-CH2-4-No 2 N1M-2
-12-CH2-4-No. Cu3) Thioacetothiophenone system R1 represents an alkyl group, an aryl group, R2 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, or a benzo condensation system, and M represents Cu, Ni or Pd.

Specific example, No, RI R2
MM-3-I CHa HN1M-3-2
C2H54-CH3N1 M-3-3C6H54-C2H6N1 M-3-44' -(CH3)2N -C6H4-HN
1M-354'-CI-CsH4-4-CH3N1M
-3-6CH34-CH3Pd M-3-7C2H, 4-CI PdM-3-8C
H34-No 2Ni M-3-9C6H5C6H5Ni 4) Acetothiophenone system R1 is an alkyl group, aryl group, R2 is a hydrogen atom, No1
Represents a 0gen atom, an alkyl group or a benzo-fused group,
M represents Cu, Ni, or Pd.

Specific example, No. R1R2MM-4-I
CH3HCu M-4-2C2H54-CH3Cu M43 CH3HN1 M-4-4C3H? 4-CH3NiM 45
(CH2)5CH3C6H5N1M 46 (CH2
)? CH3C6H5N1M-4-7C2H55,6-C
6H4N1M-4-8CH3I Pd M-4-9(C)I 2) 8CH34-Cl
Pd5) Oxyxanthion system R3 represents a hydrogen atom, a halogen atom or an alkyl group, and M represents Cu or Ni.

Specific example pJ□, RIMM-5-IH
Cu M-5-2HNi M -5-34-CH3Ni 6) Pyromeconic acid system R1 represents a hydrogen atom or an alkyl group, and M is Cu.

Represents Ni, Co or Mn.

Specific example, No. R1MM-6-IHM
n M-6-2HNi M-6-32-C2H5Ni 7) Bis-dithioninickel system RI+R2 may be substituted or unsubstituted alkyl group, acyl group or aryl group, or R,, R2 may form an aromatic ring. good. M represents Cu, Ni, Co or Pd. In this case, M has a negative charge and may have a counter cation.

No, R, R2M M-7-I C6H5C6H5Cu M-7-2C6H5C6H5N1 M-7-3p-(C2H5)2N-C6H4C6H5N
1M-7-4p -(CH3)2N-C6H4C6H5
N1M-7-5CH3Co CH3C
o N1M-7-6-CH=CH-CH=CH-N
1M-7-7-CH=C-C=CH-NiCI CI M-7-8-CH=C-CH=CH-NiN(C2H6
)2 8) Mercaptobenzazole system R1 is a sulfur atom, a substituted or unsubstituted amino group, an oxygen atom or a thioketone group, R2 is a hydrogen atom, an alkyl group,
It represents a halogen atom or an amino group, and M represents Zn, Cu or Ni.

No, R, R2M M-8-10HZn M-8-205-CH3N1 M-8-3SHNi M-8-4S 5-CI N1M-8
-5S 5-CH3N1M-8-6S
4-CH3NiM-8-7S
5-(CH5)2N N1M-8-8NHHN1 M-8-9NH5-CH3N1 M-8-10NCH3HN1 M-8-11NH6-C2H5N1 M-8-12C=S HNi9) Hydroxamic acid system R is an alkyl group, OK- represents a ru group or a styryl group,
M represents Cu, Ni or Co.

No, RM M-9-I C3H7CuM-9-2C6
H5N1 M-9-3C6H5CH=CH-N1 M-9-4CI-C, H4CH=CH-Ni10) Biscyclopentadiene system R1 represents a hydrogen atom, a halogen atom, an alkyl group, an acyl group, or an aryl group, and M is Represents Ni or Zr.

No, R, M XM-10-I
HNi-M-10-2HZr
CI M-10-3' CH3Co Ni
-M-10-4CI Ni -M
-10-5' C3H, Ni -11) Nitrosohydroxylamine system R1 represents an alkyl group or an aryl group, and M represents Cu, Ni or CO.

No, R) MM-
11-I C3H7CuM-11-2C3H
-t N1M-11-31)-(CH
3) 2N C6H4CuM-11-4p-(CH3)2
N-C6H4-Ni12) Dioxime system 20H R,, R2 represents an alkyl group or an aryl group, and M represents Ni.

No, R, R2M M-12-I CH3CH3N1M-12-
2C2H5C2H5N1 M-12-3C6H5C6H5Ni 13) Glyoxime type R,, R2 may be an alkyl group, an amino group, an aryl group or a furan group, or R3 and R2 may form an alicyclic compound. M represents Ni.

No, R1R2 M-13-I NH2NH2 M-13-2CsH,vt C6H5
M-13-3-Ross M-13-4-CH2CH2--CH2CH2-(R1
and R2 combine to form a ring) M-13-5CH3CH3 M-13-6C2H, C2H.

14) Compounds R and R2 shown by the following formula are hydrogen atoms, halogen atoms or alkyl groups, X is an oxygen atom or a sulfur atom, and M is Ni.

No, R1R2X M-14-IHHO M-14-25-CH3m-CH30 M-14-34-CH3m -CH30M-14-45
-C1p-C1O M-14-5HH3 M-14-65-CH3m-CH35 M-14-74-CH3m-C2H55M-14-85
-C1p-c 2H5S15) Compound R represented by the following formula, R2 represents a hydrogen atom, an alkyl group, a halogen atom or a nitro group, X represents an oxygen atom or a sulfur atom, M represents ■Ni, and Y represents a quaternary ammonium cation. .

No, R, R2X M-15-13-CH3I 0M-15-23
-CI 4-CH30M-15-34-No
24-CH30M-15-4H4-CH35 M-15-53-No24-C2H55R is an amino group,
M represents Cu, Ni, Co or Pd.

No, RM M-16-1(C4H++) 2 N
N1M-16-2 (C, Hll) 2N
Ni17) Anthranilic acid system R1 is a hydrogen atom, a halogen atom, an alkyl group, an acyl group, a nitro group, or an alkoxyl group, and M is Zn or Cu.

Represents Ni or CO.

No, R1M M-17-IHCu M-17-24-CI Ni M~17-3 4-No 2 N1M-
17-45-CH3Ni By combining such a metal chelate compound and a dye, it was possible to increase the reflectance, improve storage stability, and obtain a high C/N value. Such a 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 variety of resins. Specifically, cellulose esters such as nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose valmitate, cellulose acetate/propionate, cellulose acetate φ butyrate, methylcellulose, Cellulose ethers such as ethyl cellulose, propyl cellulose, butyl cellulose, polystyrene, polyvinyl chloride,
Vinyl resins such as polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone, copolymer resins such as 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-2-1,4-cyclohexylene dimethylene carbonate), poly(ethylenedioxy-3,3'-phenylene thiocarbonate), poly)4,4'-isopropylidene-diphenylene carbonate-terephthalate), poly (4,4'-isopropylidenediphenylene, carbonate), poly(4,4'-5ee-
butylidene diphenylene carbonate), poly(4,4
polyarylate resins such as '-isopropylidene diphenylene carbonate-block-oxyethylene),
Alternatively, polyamides, polyimides, epoxy resins, phenol resins, polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene can be used.

Organic solvents that can be used during coating should be in a dispersed state or
Or, it depends on whether it is in an amorphous state,
Generally, alcohols such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone,
Ketones such as cyclohexanone, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, methyl acetate, ethyl acetate, Esters such as butyl acetate, chloroform,
Aliphatic halogenated hydrocarbons such as methylene chloride, dichloroethylene, carbon tetrachloride, and trichlorethylene, or aromatics such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, and anisole can be used.

Coating methods include dip coating, spray coating, spinner coating, bead coating,
This can be carried out using a coating method such as a Mayer 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, polymethyl methacrylate, etc. are used. The substrate usually has a groove for tracking, and may further have an undercoat layer thereon to improve adhesion to the recording layer or improve solvent resistance.

According to the present invention, an optical information recording medium with increased reflectance, stable tracking, high C/N ratio, and good storage stability can be obtained.

Hereinafter, examples of the present invention will be given and explained in detail.

〔Example〕

An undercoat layer (100 to 200
Then, a recording layer having a film thickness of 800 to 1,000 layers was formed using a material consisting of a combination of a dye and a metal chelate compound shown in Table 1 below using a prescribed solvent.

The recording medium obtained in this manner was subjected to recording using a semiconductor laser beam of 830 nm from the substrate side at a recording frequency of 2 MHz, a rotation speed of 180 Or p m, and a recording power of 8 mW.
, write and read with a read power of 0 and 6 mW, and the read waveform was analyzed by spectral analysis.
/N value was measured.

Next, the same recording medium was heated for 10 minutes at 60°C and 90%RH.
A storage acceleration experiment was performed by leaving it for 00 hours, and the reflectance C/N
The value was measured. The results are shown in Table 2.

(Table 1) (Table 2) [Effects of the Invention] As described above, according to the present invention, an optical film that increases the reflectance of a recording film and improves its storage stability by using a polymethine dye and a metal chelate compound. It is possible to provide an information recording medium.

Claims (2)

[Claims] (1) An optical information recording medium characterized in that the recording layer contains a polymethine dye represented by the general formula (1) and a metal chelate compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) R_1, R_2, R_3, R_4 and R_ in formula (1)
5 means hydrogen, alkyl group, substituted alkyl, cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, aryl, substituted aryl, styryl, substituted styryl, heterocycle or substituted heterocycle, m is 0 or 1, n is 0, 1 or 2, and X^■ means an anion group. (2) The metal chelate compound is Zn, Cu, Ni, Co,
The optical information recording medium according to claim 1, which is a metal chelate compound of Mn, Pd, and Zr.