JPS5955794A - Optical recording medium - Google Patents

Abstract

PURPOSE:To improve preservability and regeneration deterioration due to the light in a red - near-infrared region, by providing a recording layer containing carbocyanine coloring matter and a singlet oxygen quencher on a support to form an optical recording medium. CONSTITUTION:Carbocyanine coloring matter shown by a formula I (wherein phi and psi are a thiazole ring or a selenazole ring with which a benzene ring or a naphthalene ring may be condensed, L is a linkage group for forming mono-, di-, tri- and tetracarbocyanine, X<-> is an anion and m is an integer of 0 or 1) and a singlet oxygen quencher such as a transition metal chelate compound are dissolved in a solvent to prepare a recording layer forming liquid. This recording layer forming liquid is applied to the surface of a substrate comprising various kinds of resins or glass in a thickness of about 0.03-2mum to form an optical recording medium having a recording layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to an optical recording medium, particularly a heat mode optical recording medium.

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out.

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. Some devices perform writing by forming small holes, record information using the pits, and read out information by detecting the pits with readout light.

As an example of such bit-forming media,
A recording layer made of a light-absorbing dye is formed on the substrate to form pits by melting the dye, or a recording layer containing a self-oxidizing compound such as nitrocellulose and a light-absorbing dye is formed. , those that form pits by decomposing nitrocellulose, etc., and those that have a recording layer made of thermoplastic resin and light-absorbing dye and form pits by melting the resin and dye are known. .

By the way, carbocyanine dyes are known as one of the light-absorbing dyes.

However, when using carbocyanine dyes, the storage stability of the medium against light and the storage stability after recording are poor, and when stored in the presence of light, it becomes impossible to write or the S/N ratio deteriorates. Not practical. In particular, when the thickness of the recording layer decreases to less than about 0.2 μm, such inconvenience becomes extremely noticeable.

Incidentally, deterioration caused by light is generally considered to be due to light in the ultraviolet region, and in order to improve light resistance, it is considered to include an ultraviolet absorber in the recording layer or the like. However, it was confirmed that even if the recording layer containing the carbocyanine dye contained an ultraviolet absorber, the light resistance did not improve much.

Therefore, the present inventors investigated the wavelength dependence of light resistance and found that it is particularly light with wavelengths in the red to near-infrared region that worsens the storage stability of recording layers containing carbocyanine dyes. It has been found.

Due to the above-mentioned circumstances, in media using carbocyanine dyes, reproduction degradation is large when readout light in the red to near-infrared region is used, and repeated irradiation with readout light causes the readout S/N ratio to decrease. It is deteriorating.

■ Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide a carbocyanine dye that has improved storage stability and reproduction deterioration against light in the red to near-infrared region. An object of the present invention is to provide an optical recording medium having a recording layer.

The present inventors have conducted various studies for five purposes,
Deterioration in storage stability and increase in regeneration deterioration are caused by the oxidative deterioration of carbocyanine dyes caused by singlet oxygen generated when carbocyanine dyes are excited by red or near-infrared light and transfer energy to ground state oxygen. I got the idea that maybe it was.

Therefore, the present inventors found that by incorporating a -heavycyclic oxygen quencher into the recording layer, the storage stability and playback deterioration were significantly improved, and the present invention was completed.

That is, the present invention is an optical recording medium characterized by having a recording layer containing a carbocyanine dye and a -heavycyclic oxygen quencher on a substrate.

A second invention is an optical recording medium characterized by having a recording layer on a substrate that includes a carbocyanine dye, a -heavycyclic oxygen quencher, and an autooxidizing compound or a thermoplastic resin.

■Specific structure of the invention Hereinafter, the specific configuration of the present invention will be explained in detail.

The light-absorbing dye in the present invention is a carbocyanine dye.

Although various carbocyanine dyes may be used, the effects of the present invention are particularly enhanced when the compound is represented by the following formula.

Formula (I) Φ-L=W (X-)m In the above formula [II, Φ and V are each a thiazole ring, an oxazole ring, a selenazole ring, or an imidazole ring in which a benzene ring or a naphthalene/ring is fused. Or the residue of the pyridine ring.

In this case, Φ and W are such that Φ has ten charges on the N atom of each of these rings and 1ON atom is neutral. Each of them may be the same or different from the other, and various substituents may be bonded to each other.

Among these, Φ and W are preferably the same, and particularly preferably the following formulas (n) to Cx+t). In addition, in the following, it is expressed in the form of Φ.

[l) R□ (fit) K engineering [IV) R engineering [7] (R').

[■]

[■] [■] R Engineering [■] (1尤') w H Engineering In the above, R Engineering and R2 each represent a substituted or unsubstituted alkyl group or ant, - group.

In this case, the number of carbon atoms in the alkyl group is preferably 1 to 5, and preferred substituents include a sulfonic acid group, an alkylcarboxyoxy group, an alkylamido group, an alkyloxy group, and a hydroxyl group. can. Note that when m, which will be described later, is 0, the R element of Φ has one charge.

Also, R1, R2, R3, R4, R5, R', R6
', R7, R8, R9 and R10 each have a substituent, such as an alkyl group, an aryl group, a heterocyclic residue, a halogen atom, an alkoxy group, an alkylthio group, an alkylhydroxycarbonyl group, a carboxylic acid group, etc. It is preferable that there be. And p, ql r, S, tl u
, u', v1w%x, y and 2 are each an integer of 0 or 1 or more, but usually about 0 to 4.

On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye, but especially a linking group of the formula [X
It is preferable that it is any one of [M] to [藷].

Formula (xnt) CH,=CH-Cl-1=CH-C=CH-CH=CH
-CH formula 13) CH=CH-CH, =C-CH-C
H-CH■ Formula [■) CH= CH-C= CH-CH formula [XK
] CH-C=CH-CH Here, Y represents a hydrogen atom or a monovalent group. In this case, the valent group includes a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, a dimethylamino group, a diphenylamino group, a methylphenylamino group, a morpholino group, an imidazolidine group, and an ethoxycarbonylpiperazine group. Preferable examples include disubstituted amine groups such as, alkylcarbonyloxy groups such as acetoxy groups, alkylthio groups such as methylthio groups, cyano groups, nitro groups, and 710 gene atoms such as Br and C1.

In addition, among these formulas [■] to [X[X], tricarbocyanine linking groups, particularly formulas (XIV) to [■] are preferred.

Further, X- is an anion, and preferable examples thereof include ■-5Br-1CtO":, BP, -1. Note that m is O or 1, but when m is 0, usually Φ
The R element has a single charge and becomes an inner salt.

Next, specific examples of the light-absorbing dye of the present invention will be given, but the present invention is not limited thereto.

Dye layer Φ, FR,, R2R1~RIO
DI CI [)
C2H,4-CHD2
(I[)
CH34-CHD3
[LII': l C, H, -D4
[11D C2H35-Ct
D5 [■] CQH55-OC
HD7 (Il[) C2H
6-D8 (nD CaI2
-D9 (1:]
C2H6-DIO(IT) C2H
,-L Y
X(:XIV) HI [x■) HI [X■] HC6O [Xv)N(C6H5)2CLO Cxw) HI [X■]H■ [X■] ■(x■)
HI [:xm) HCa (XIV:] CH3I D1l (III:) C2H5
-DI2 ([) C2H3-D
I3 [1[[]]02H6-
D14 (■:] (CH2)30CO
CH3-Dls Crv) CH
2CH20H5-CtD16[v]CQH6- DI 7 CW) "2H5-
DI8 [■] C2H3- DI9 (W) ” C2H6-D2
0 [■:] C2H5-509- [:XVII] HI [X product] H work (XI) I
(XV) N(C6H5)2C/=O.

[Cave] HC6O.

(XIV) HC1O.

[■) Hr [XV:l 0COOC2H,CtD[XV]
0CH5I [XIV) HI (1 D21 [■)
CH2CH20H-D22
(,K)
CQH5-D23 [K]
(CH2)30COCH3-D24
(X) C2H5-D25
(X:] CH2CH2CH25o3H-
D26 (X) C2H6-
D27 (M) ' 1lH
5-D28 [Abyss] C2H6
- [V″l H, C tilt.

CITV) HI [X■]0COOC2H5C6O4 [X■] HI [πr’3　　　　　N(C,H,)　, coo.

(XV) N (C6Hl,)2I Hitomi)
HCtO number [correct] HCtD.

Such carbocyanine dyes have been used in laser research 8 (4).
) Comprehensive list of organic compounds for dye lasers, Daio Organic Chemistry (Breakfast Shoten), Nitrogen-Containing Heterocyclic Compound IP432, etc., and can be synthesized by known methods.

Such a dye constitutes the recording layer by itself. Alternatively, it is contained in the recording layer together with a self-oxidizing compound or a thermoplastic resin.

In the latter case, crystallization in the layer is suppressed and the physical properties of the film are better than when the recording layer is formed using a dye alone. □ The self-oxidizing compound contained in the recording layer undergoes oxidative decomposition when the temperature rises.

Examples of such self-oxidizing compounds include Japanese Patent Application No. 55
Among them, nitrocellulose is preferred.

In addition, the thermoplastic resin contained instead of or in addition to the self-oxidizing compound softens as the temperature of the light absorber that absorbs the recording light increases. Various known materials can be used as the material.

Among these, thermoplastic resins that can be particularly preferably used include the following.

I) Polyolefin polyethylene, polypropylene/, poly4-methylbe/ten-1, etc.

ti) Polyolefin copolymers, such as ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-acrylic acid copolymers,
Ethylene-propylene copolymer, ethylene-butylene/-1
copolymers, ethylene-maleic anhydride copolymers, etele/propylene terpolymers (EPT), etc.

In this case, the polymerization ratio of the comonomers can be arbitrary.

i) Vinyl chloride copolymer, for example, vinyl acetate-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, acrylic ester or methacrylic ester and vinyl chloride copolymer, acrylonitrile-vinyl chloride copolymer, vinyl chloride ether copolymer,
Ethylene or propylene/-vinyl chloride copolymer, ethylene-vinyl acetate copolymer grafted with vinyl chloride, etc.

In this case, the copolymerization ratio can be arbitrary.

iv) Vinylidene chloride copolymer Vinylizo chloride/-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylizo chloride/-butadiene-vinyl halide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

■) Polystyrene vi) Styrene copolymer For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMAN resin), Styrene/-acrylic ester-acrylamide copolymer, Styrene/-butadiene copolymer (5
BR), styrene-vinylidene chloride copolymer, styrene-methyl methacrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

vi) Styrenic polymers such as p-methylstyrene, 2,5-dichlorostyrene, α,β-vinylnaphthalene, α-vinylpyridine,
Acenaphthene, vinylanthracene, etc., or copolymers thereof.

vii) Kumalo/-indene resin Chroman-indene-stere/copolymer.

tx) Terpene resin or picolite For example, terpene resin which is a polymer of limonene obtained from α-pinene, or picolite obtained from β-pinene.

X) Acrylic resin Particularly preferred are those containing an atomic group represented by the following formula.

Formula　　　　　R□.

] 100-C- C-0a2゜1 In the above formula, R□. represents a hydrogen atom or an alkyl group, and R2o represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R. is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and % is preferably a hydrogen atom or a methyl group. Also,
R2o may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 4 carbon atoms, and when R2o is a substituted alkyl group, a substituted alkyl group The group is preferably a hydroxyl group, a halogen atom, or an amino group (particularly a dialkylamino group).

The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one type of atomic group represented by the above formula is used. Alternatively, an acrylic resin is formed by forming a homopolymer or copolymer having two or more repeating units.

xi) Polyacrylonitrile xi) Acrylonitrile copolymer such as acrylonitrile-vinyl acetate copolymer, acrylnitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylic Nitrile-vinylpyridine copolymer, acrylonitrile-methyl methacrylate copolymer,
Acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

xfI) Dia7ton/acrylamide polymer Dia7ton acrylamide polymer made by reacting aceto/acrylic nitrile with aceto/acrylamide.

xtv) Polyvinyl acetate W) Examples of vinyl acetate copolymers Copolymers with Eva, acrylic ester, vinyl ether, ethylene, vinyl chloride, etc.

The copolymerization ratio may be arbitrary.

X! A) Polyvinyl ether, such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc.

New) Polyamide In this case, the polyamides include nylon 6, nylon 66, nylon 610, nylon 612, nylon 9,
In addition to regular homonylons such as nylon/11, nylon 12, and nylon 13, copolymers such as nylon 6/66/610, nylon 6/66/12, and nylon/6/66/11, and modified in some cases. It may also be nylon.

i) polyesters, for example, various dibasic acids such as aliphatic dibasic acids such as oxalic acid, cono-phosphoric acid, maleic acid, adipic acid, sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid; Condensates and co-condensates with glycols such as ethylene glycol, tetramethylene glycol and hexamethylene glycol are suitable. Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable.

Furthermore, modified glybutal resin, which is obtained by esterifying and modifying glybutal resin, which is a condensation product of phthalic anhydride and glycerin, with a fatty acid, a natural resin, etc., is also preferably used.

xix) Polyvinyl acetal resin Both polyvinyl formal and polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol are preferably used.

In this case, the degree of acetalization of the polyvinyl acetal resin can be arbitrary.

xx) Polyurethane resin Thermoplastic polyurethane resin having urethane bonds Particularly preferred are polyurethane resins obtained by condensation of glycols and diisocyanates, especially polyurethane resins obtained by condensation of alkylene/glycol and alkylene diisocyanate.

xxi) Polyether styrene formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene/oxide, etc.

) oci) cell four-s derivative Organic acid esters, ethers or mixtures thereof.

Cancer-free polycarbonate such as polydioxydiphenylmethane carbonate,
Various polycarbonates such as polydioxydiphenylethane carbonate and dioxydiphenylpropane carbonate.

A blend of two or more of the above i) to)othI),
or blended with other thermoplastic resins.

Note that the self-oxidizing compound and the thermoplastic resin may have various molecular weights.

Such an autooxidizing compound or thermoplastic resin and the above-mentioned dye are usually formed in a wide range of weight ratio of 1:0.1 to 100.

Furthermore, the recording layer contains a -heavycyclic oxygen quencher.

Various types of single-ring oxygen quenchers can be used, but in particular, they are expected to significantly improve stability and light resistance, increase absorption of long-wavelength writing laser light, and further reduce reproduction deterioration. A transition metal chelate compound is preferable because it has good compatibility with the dye and has good compatibility with the dye.

In this case, as the central metal, Ni, Co, Cu, Iori, etc. are preferable, and the following compounds are particularly preferable.

In addition, as a transition metal chelate compound, 700 to 85
Those with absorption at 0 nm, especially 700 to 8
Preferably, the material has a maximum absorption wavelength of 50 nm.

1) Acetylacetonate chelate QI N1(u) Acetylacetonate Q2 Cu(I
[)Acetylacetonate Qa Mn(l[)Acetylacetonate Q4 Co(n)Acetylacetonate 2
) Bisditheo-α-diketone system Here, carp) to a4) represent an alkyl group or an aryl group, and M represents a divalent transition metal atom.

Q5 N1 (i) dithiobenzyl Qe Ni (1) ditheobiacetyl B 3) Hi, x, phenyldithiol system here R (5
1 and α6) represent an alkyl group such as a methyl group, or a trivalent atom such as Ct, and M represents a divalent transition metal atom such as N1.

Moreover, further coordination may be performed above and below M in the above structure.

As such, the following are commercially available.

Q9 PA-1001 (product name manufactured by Mitsui Toatsu Fine Co., Ltd.) QIOPA-1002 (same as above) Qll PA-1003 (same as above) Q12 PA-1005 (same as above) Q13 PA-1006 (same as above) 4) Salicylaldehyde In the oxime system, R(7) and 8) represent an alkyl group, and M represents a divalent transition metal atom.

Q14 N1(IF) O-(N-isopho Hill*
yvmuimidoyl)phenol Q15 N1(If)0-(N-dobumylformimidoyl)phenol Q16 Co(I) 0-(N-dodecylformimidoyl)phenol Q17 Cu(I)O-(N-dodecylformimide il) phenol.

Q18 Nt(u) 2 , 2′-(tritetramethylidine in ethylene bis)]-diphenol Q19 Co(II) 2 , 2′-[: trilomethylidine in ethylene bis)]-diphenol Q20 Nt(n) 2 , 2'-[: 1.8-s7
Terenbis(nitritetramethylidine)]-diphenol Q
21 N1(H)-[N-phenylformimidoyl]phenol Q22 Co(II)-[N-phenylformimidoyl]phenol Q23 Cu(1)-(N-phenylformimidoyl]phenol Q24 N1(II) salicylaldehyde phenylhydrazone Q25 N1 (1) salicylaldehyde oxime 5) thiobisphenolate chelate trace υ In particular, M is the same as above and R (91 and RQI
represents an alkyl group, and C4) represents an amino group.

Q26 N1 (IF) n-buty/I77 mino[:2.
2'-thiobis(4-tert-octy#)-phenolate] Q27 N1(II) n-butylamide/ (: 2
, 2'-thiobis(4-tert-octyl)-phenolate] Such a -1 term oxygen salt/char is synthesized according to a known method.

The -heavycyclic oxygen quencher is generally 0.05 to 12 mol per mol of the dye, particularly IC 0.1 to 1.
It is contained in an amount of about 2 moles.

In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method, and the thickness thereof is generally about 0.03 to 2 μm. Alternatively, when forming the recording layer using only the dye, vapor deposition, sputtering/gluing, etc. may be used.

In addition, such a recording layer may contain other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, etc.

Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, and ethers such as methyl cellosolve and ethyl cellosolve. , aromatic compounds such as toluene and xylene, and halogenated alkyl compounds such as dichloroethane.

The material of the substrate on which such a recording layer is provided is not particularly limited, and may be any of various resins, glass, ceramics, metals, etc.

In addition, the shape varies depending on the purpose of use, such as tape, disk,
It may be a drum, a belt, etc.

Note that the base body may have a base layer such as a reflective layer, a heat storage layer, etc., as necessary.

In addition, on the recording layer, if necessary, a reflective layer that functions as a back surface when using a transparent substrate, various uppermost protective layers, etc.
It is also possible to provide a single layer of half-mirror.

The medium of the present invention may have the recording layer described above on one surface of such a substrate, or may have recording layers on both surfaces thereof. In addition, two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, which is then sealed tightly to prevent dust and scratches. You can also do it like this.

(2) Specific Effects of the Invention The medium of the present invention is irradiated with recording light at a pulsed pressure while traveling or rotating. At this time, due to the heat generated by the dye in the recording layer, the self-oxidizing compound decomposes or the thermoplastic resin or dye melts, forming pits.

In this case, particularly when a tri- or tetracarbocyanine dye is used, very good writing can be achieved when a recording semiconductor laser, diode, etc. with a wavelength of 750.780.83 Q nm is used.

The pits thus formed are read out by detecting reflected or transmitted light, especially reflected light, of the readout light of the above wavelength while the medium is running or rotating.

Note that when a thermoplastic resin is used for the recording layer, the pits once formed in the recording layer can be erased with light or heat and then rewritten.

Furthermore, a He--Ne laser or the like can also be used as the recording or reading light.

■Specific Effects of the Invention According to the present invention, even when stored in the presence of red to near-infrared light, the singlet oxygen generated by the excited state of the carbocyanine dye is converted to the triplet state by the quencher. Since the conversion is effective, the oxidative deterioration of the carbocyanine dye is extremely small, and the raw and archival storage properties are significantly improved.

Further, reproduction deterioration due to read light is also extremely small.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Example 1 Using dye D and resin R1-heavycyclic oxygen quencher Q shown in Table 1 below, they were dissolved in a predetermined solvent in the proportions shown in Table 1, and placed on an acrylic disk substrate with a diameter of 15 crn. A layer of 0.2 μm thick was applied to obtain various media.

In this case, in Table 1, NC has a nitrogen content of 11,5 to
12.2%, nitrocellulose with a viscosity of 20 seconds based on JIS K6703.

In addition, CI is coumaro/indene resin (manufactured by Nippon Steel Chemical Co., Ltd. V-120, number average molecular weight 730), NY is 6,6-nylon (number average molecular weight 30,000), and EC is ethyl cellulose (number average molecular weight 30,000). 10,000, degree of acetylation 30%) and PS each represent polystyrene (number average molecular weight 30,000).

Furthermore, the dyes used were the waste ones exemplified above, and as the comparative dye A, near-infrared absorbing dye PA-1006 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) shown as Quencher-Q13 was used. .

In addition, the quenchers used are shown as scraps of those exemplified above.

Table 1 also lists the weight ratio of R/D and the molar ratio of Q/D.

For each medium created in this way, add this to 1800
While rotating at rI) m, the AIQaAs-GaAs semiconductor laser recording light (830 nm) was focused to a diameter of 1μ.
See, writing was performed by irradiating in a pulse train at a predetermined frequency.

After this, 1 mW (7) semiconductor laser (830 nm
) The reading light was irradiated with pulses of 1 μsec width and 3 KHz, and the initial peak-to-peak S/N ratio on the disk surface and the S/N ratio after 5 minutes of irradiation were measured.

Furthermore, apart from this, write the medium in the dark,
It was stored for 5000 hours under conditions of 60° C. and 90% relative humidity, and the S/N ratio after storage was measured.

Further, the medium after writing was irradiated with a 250 W infrared lamp at a distance of 40 meters for 5 hours, and the S/N ratio after irradiation was measured.

These results are shown in Table 1.

From the results shown in Table 1, it can be seen that the medium layers 2 to 7 and 11 of the present invention
,] 3.15.17.19 and comparison medium/168-1
In comparison with 0.12.14.16.18, the effect of the present invention is clear.

Example 2 Using the medium 7g611.13, ]5.17.19 of Example 1, writing was performed in the same manner as in Example 1, and then the medium was heated at 150°C for 15 seconds using an infrared heater to erase. As a result, it was confirmed that each medium could be successfully erased and rewritten multiple times.

Applicant Tokyo Denki Kagaku Kogyo Co., Ltd. Agent Patent Attorney Yo Ishii - (12) Procedural amendment (spontaneous) June 23, 1981 1, Indication of case 1982 Patent Application No. 166832 2, Title of the invention Optical recording medium 3, relationship with the case of the person making the amendment Patent applicant office
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) Representative of TDC Co., Ltd.
Kan Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
Goyabe Building 1st Floor Telephone: 988-16806 The statement in column 13, "Detailed Description of the Invention" in the Statement of Contents of Amendment is amended as follows.

Mnj means 1rNi, Co, Cu, Mn.

Correct Pd and Ptj.

II) The description from page 27, line 2 to page 33, line 2 is corrected as follows.

“1) Acetylacetonate chelate QINi (I
I) Acetylacetonate Q2 Cu (n) Acetylacetonate Q3 Mn (m) Acetylacetonate Q4 Co (II) Acetylacetonate 2) Bisdithio-α-diketone system where R (IL R (4) is substituted or unsubstituted alkyl group or aryl group, M is Ni, C
represents a transition metal atom such as o, Cu, Pd, Pt, etc.

In this case, M has a single charge and may form a salt with a cation such as a quaternary ammonium ion.

Q5' Ni (II) dithiobenzyl Q6Ni (
II) Dithiobiacetyl N (C,H8).

3) Bisphenyldithiol system (5) (8) Here, R and R represent an alkyl group such as a methyl group, or a halogen atom such as C1, and M is Ni or Co.

Represents a transition metal atom such as Cu, Pd, or Pt. Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with a cation, and further, other ligands may be bonded above and below M.

Examples of this include the following:

QIOPA-1001 (trade name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (same as Ni-bis(toluenedithiol)tetra(t-butyl)ammonium) Q12 PA-1003 (same as above) Q13 PA-1005 (same as above) Same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 FA-1006 (same as above Ni-bis(trichlorobenzenedithiol) tetra(t-butyl)ammonium) Q15 Co-bis(benzene-1,2 -dithiol)tetrabutylammonium Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q17 Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18 Ni-bis(O -xylene-4,5-dithiol)tetrabutylammonium Q19 Ni-bis(5-chlorobenzene-1,2-
dithiol) tetrabutylammonium Q20 Ni-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol) ) Tetrabutylammonium 4) Salicylaldehyde oxime system (7) (8) Here, R and R represent an alkyl group, and M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as PL.

Q22 Ni(II)o-(N-isopropylformimidoyl)phenol Q23 N1(II)o-(N-dodecylformimidoyl)phenol Q24 Co(II)o-(N-dodecylformimidoyl)phenol Q25 Cu (II) o -(N-dodecylformimidoyl)phenol Q26 N1(II)2.2'-(trilomethylidine on ethylene bis)) lphenol Q27 Co(II)2.2"-(z ethylene bis and trilomethylidine)] -Diphenol Q28 Ni (II) 2.2”-(1,8
-naphthylenebistrilomethylidine)]-diphenol Q29 Ni (IT)-(N-phenylformimidoyl)phenol Q30 CO(H)-CN-7ethylformimidoyl)phenol Q31 Cu (IT) (N-phenyl (formimidoyl) phenol Q32 N1(II) salicylaldehyde phenylhydrazone Q33 N1(II) salicylaldehyde oxide 5)
Thiobisferrate chelate system (9) Here, M is the same as above, R and R (10) represent an alkyl group, and M has a single charge and forms a salt with a cation. Good too.

Q34 Ni (II) n-butylamino [2゜2
'-thiobis(4-tert-octyl)-ferulate) (Cyasorb-UV-1084 (American Cyanamid Co., Ltd.)) Q35
Co(II) n-butylamino[2゜2'-thiobis(4-tert-octyl)-ferulate] Q36 Ni(II) -2,2'-thiobis(
4-tert-octyl)-ferrate 0 ■) On page 38, line 15, it says FQ13j,
1rQ14-j.

■) In Table 1 on pages 40-41, f
Q20j to rQ28j 4. :, 1rQ10j ['
Correct Q11j and FQ13j to fQ14j.

Claims (1)

[Scope of Claims] 1. An optical recording medium comprising a recording layer containing a carbocyanine dye and a -1 term oxygen quencher on a substrate. 2. The optical recording medium according to claim 1, wherein the carbocyanine dye is a compound represented by the following formula [E]. Formula CI) Φ-t, =V/(X-)m [In the above formula [I], Φ and W are each a thiazole ring, a selenazole ring, an imidazole ring, or an imidazole ring to which a benzene ring or a naphthalene ring may be fused Represents a residue of a pyridine ring, L is
represents a connecting group forming mono-, di-, tri- or tetracarbocyanine; X- represents an anion; m is O or an integer of 1; 3. The optical recording medium according to claim 1 or 2, wherein the oxygen quencher is a transition metal chelate compound. 4. An optical recording medium characterized by having a recording layer on a substrate containing a carbocyania dye, a -1 term oxygen quencher, and a self-oxidizing compound or a thermoplastic resin. 5. The optical recording medium according to claim 4, wherein the carbocyanine dye is a compound represented by the following formula [1]. Formula CI) Φ-I, = i (x-)m (In the above formula [I], Φ and W are each a thiazole ring, an oxazole ring, to which a benzene ring or a naphthalene ring may be fused,
Represents a residue of selenazole ring, imidazole ring or pyridine ring, L represents a linking group for forming mono-, di-, tri- or tetracarbocyanine, X- represents an anion, m represents O or 1. is an integer. 6. The optical recording medium according to claim 4 or 5, wherein the doublet acid cumulative quencher is a transition metal chelate compound.