JPS5967092A - Optical recording medium - Google Patents

Abstract

PURPOSE:To improve the paint film property and the preservability of a recording layer in an optical recording medium with a heat mode having a recording layer containing a carbocyanine having an indole ring produced by condensation of an aromatic ring by providing a recording layer containing a light absorbing pigment of a specified compound on a substrate. CONSTITUTION:A light absorbing pigment as represented by the formula I is contained in a recording layer. the benzoindole ring produced by the condensation of Q and Q' is preferably based on the formula II or the like. Where, R4 represents halogen atom or the like and (p) 0 or 4 or less. On the other hand, R1 and R1' each represent a substituted or unsubstituted alkyl group and the atomic number of carbon shall be 4 or more, preferably 6-18. R2 and R3 each represent an alkyl group and the atomic number of carbon is preferably 1. On the other hand, L represents a linked group for forming carbocyanine. In addition, X<-> is an anion and (m) 0 or 1.

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.As a result, research and development efforts are being conducted to develop glazed optical recording media.

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. Writing is performed by forming all of the small holes, all of the information is recorded using these pits, and reading is performed by detecting these pits with read light.

1f+11 of such pit-forming media
As a recording layer, a recording layer made of a light-absorbing dye is formed on a substrate, and the dye is completely melted to form a focus, or a recording layer containing a self-oxidizing compound such as nitrocellulose and a light-absorbing dye is used. There are those in which a recording layer consisting of a thermoplastic resin and a light-absorbing dye is applied, and pits are formed by melting the resin and dye. etc. are known.

By the way, one of the light-absorbing dyes is carbocyanine dye.

However, when using carbocyanine dyes that have typically used thiazole rings, benzothiazole rings, naphthothiazole rings, benzoselenazole rings, benzoxazole rings, etc. at both ends of the vinylene chain, the solubility is low, and the resin Since the compatibility with the paint is low and the surface properties of the coating film are poor, the reflectance is low and the readout C/N ratio is low.

Therefore, as a result of various studies, the present inventors found that only when using carbocyanine dyes having an indole ring, benzoindole ring, naphthoindole ring, etc., compared to other carbocyanine dyes. We discovered that a medium with high solubility and compatibility with resins, good coating properties, high writing sensitivity, high reflectance, and high read C/N ratio could be realized, and we first proposed this idea. ing.

However, carbocyanine having an indole ring in which these aromatic rings are condensed has the disadvantage that recrystallization and bleed-out occur in the recording layer, resulting in poor raw storage and recording storage properties.

Furthermore, when forming a recording layer by itself or by being compatible with a resin, it has drawbacks such as poor coating properties.

■ Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and provides a heat mode optical recording medium having a recording layer containing a carbocyanine having an indole ring condensed with an aromatic ring. The main purpose is to improve the coating properties and storage stability of

Such an object is achieved by the following first to fourth aspects of the present invention.

That is, the first invention is an optical recording medium characterized by having a recording layer containing a light-absorbing dye represented by the following formula (I) on a substrate.

The second invention is an optical recording medium characterized in that it has a recording layer on a substrate, which comprises a light-absorbing dye represented by the following formula (1) and a resin.

A third invention is an optical recording medium characterized by having a recording layer on a substrate that includes a light-absorbing dye represented by the following formula (L) and a -heavycyclic oxygen quencher.

A fourth invention is an optical recording medium characterized by having a recording layer on a substrate that includes a light-absorbing dye represented by the following formula (1), a resin, and a -heavycyclic oxygen quencher.

1 In the above formula [1], Q and q each represent an aromatic ring such as a fused benzene ring or a fused naphthalene ring, and R1 and R1 each represent a substituted or unsubstituted alkyl group having 4 or more carbon atoms. Represents R22 stone, R32
and R'3 each represent an alkyl group or an aryl group; LU represents a linking group for forming carbocyanine; X- represents an anion; m is O or 1; F 逼 Specific Configuration of the Invention The specific configuration of the present invention will be explained in detail below.

The recording layer of the optical recording medium of the present invention contains a light-absorbing dye represented by the above formula [I]. .

In the above formula (1) (', Q and Q' may be the same or different, but are usually the same.

Various substituents can be bonded to the condensed ring formed by Q.

Among these benzoindole rings formed by condensation of Q and Q', particularly preferable ones are those shown in the following formulas (It) to [■]. In this case, the ring formed by condensing Q and 7 will be shown below.

In the above, R4 represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, an alkyloxycarbonyl group, a carboxylic acid group, etc., p is O or 4 or less, and q
Tr and S are each 0 or 6 or less.

-10,000, and R; each represents a substituted or unsubstituted alkyl group.

The number of carbon atoms of Ro and R is 4 or more, respectively. When the number of carbon atoms is less than 4, the desired effects of the present invention are not achieved.

However, if the number of carbon atoms is too large, the extinction coefficient decreases, and the quality and manufacturing cost increase, so it is preferable that the number of carbon atoms is 4 to 19. and,
When the number of carbon atoms is 5 to 18, particularly 6 to 18, even more favorable results can be obtained.

In addition, when R1 is a substituted alkyl group, preferable substituents include a sulfonic acid group, an alkylcarboxyoxy group, a halogen atom, a hydroxyl group, an alkyl-substituted amine group,
Examples include an alkyloxygalbonyl group.

Note that when m, which will be described later, is O, R1 has one charge.

Further, s R2 and Karasu each represent an alkyl group or an aryl group such as a phenyl group, preferably an alkyl group. In this case, the alkyl group is preferably unsubstituted and has 1 or 2 carbon atoms, especially 1.

On the other hand, L represents a linking fund for forming mono-, di-, tri- or tetracarbocyanine, but especially for the formula (V
It is preferable that the child be one of the younger children of l) to [■].

Formula (■) CH=CH-Cl-l=C-CH=CH-C
H formula (XI) CH=CH-CH=CH-C=CH-CH=CH-CH
Formula (XI) CH-CH-C=CH-CH formula (Xll
) CH=C-CH Here, Y represents a hydrogen atom or a monovalent group. In this case, the monovalent 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, and a methylphenylamino group.

Preferably, it is a di-substituted amino group such as a morpholino group, an imidazolidine group, or an ethoxycarbonylpiperazine group, or an alkylcarbonyloxy group such as an acetoxy group.

In addition, in these formulas (Vl) ~ [■], [■] ~ [
X] tetra- or tricarbocyanine linking group, especially (
Vl) and (■) tricarbocyanine linking groups are preferred.

Further, X'' is an anion, and preferable examples thereof include I-, Br-, Ce04-, BF4-.

Note that m is O or 1, but when m is 0, R1 usually has one 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.

D t (u) Ct□H35-
CII3D2 (R)-C4H9-CH31)
3 (U) CaH+aOCO
CH5”H3D4 (n) -c7H
,4cH2oa-CH5D5 (
layer) -C8H,, -CH5D6 (+
v) (C,H,,Coo --cH3C7H,4
COOH D 7 (IN' 〕//
CH3D8C■)-C7H14COOC2H5-C
H31)9 (IT) -C5H,, -C
H3Dlo (!V) Cs5H3□
-CH.

Dll (ff)-C, H1□-C1]3D12
(11)-C, □H34COOCH3-CH3
D] 3 (I[) C3H160
COCH3-CH5RR'L
Y X31 3 -CH3[Vl,) H1-CH5(
vi) HC, go4-CH3[v'
) H1-61□ (Vl), . ao
4-6H3(Vl) □ --CH
3[v' HBF -6H, (Vl) 1□. . 4-CH
3 [■]H.

-6H, (vt) H1 DI4 [:n) -C8H,□
-C2H5Di 5 CIt)
-C7H,, -C2H3D 16 (Ill)
-C,, LI34COOCH3-CHD17
C11)-C8H,6CH20COCH3-C
) (3D18 [harvest) -c F H35CH
3D19 [Ten]-C7H04C100CH3C
2H502Q (■)
-C7H,4CH20HCHaD 21 (I
V]-C,H,,CH20COC2H5CH3D22
(IV)-C17H14COOC2H5-CH
3D23 (IV)-C,, H2S-CH3D2
4 (IV) C7HIS
C2H3D25 (V) C7H
15CHaD 26 (V) C7H
5CH3D27 CV) Cl7H3
5CHaD 28 (V) C57
H34CH2C) COCHs CH3-C2H5
(Vl) H1 -C2H,l) H1 -CH(Vl) HC1! =O<f-λ -CHD'l) -N N-C0UC,,H,C
C04 Shiichino0□H6(Vl) HCl504-CH(V
l) HC,eO<CI(3(”
H1 = -CI(3[v■]-N/C6H5 \C6H3 -CH3(■JH1 -C2H, (VT) Hl CH3(VI) Hl CH3(■) H0ent CH3[■] Hce3o4 CH(Vl) H.

Such dyes can be easily synthesized according to the method described in Nitrogen-Containing Heterocyclic Compounds, page 1432, Dai Organic Chemistry (Breakfast Shoten).

That is, first, a corresponding indolenine such as 2,3,3-trimethylindolenine is treated with excess alkyl iodide (
When fed, it is heated with C1°H35I) to obtain an N-alkyl/drenin iodide association. This is converted into an unsaturated dialdehyde (e.g. 0HC-CH-CH-CH=
CH-CHo) and dehydration condensation using an alkali catalyst.

Such a dye can also form a recording layer alone.

Alternatively, the entire recording layer is formed together with resin.

The resin used is preferably a self-oxidizing resin or a thermoplastic resin.

The self-oxidizing resin contained in the recording layer causes oxidative decomposition when the temperature rises, but among these,
Particularly suitable is nitrocellulose.

Further, the thermoplastic resin is softened by the temperature rise of the dye that completely absorbs the recording light, and as the p1 thermoplastic resin, a publicly known Yuzu resin can be used.

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

I) Polyolefin polyethylene, polyzolopyrene, poly4-methylpentene-1, etc.

it) polyolefin copolymers such as ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-acrylic acid copolymers,
Ethylene-propylene copolymer, ethylene-butene-1
copolymers, ethylene-maleic anhydride copolymers, ethylene zolopyrene terpolymers (El)T), etc.

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

111) 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, :r
-TeV7-Vinyl acetate copolymer and vinyl chloride graft polymerized, etc.

In this case, the copolymerization ratio can be arbitrary.

iv) Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadixy-vinyl halide copolymer Nato.

In this case, the copolymerization ratio can be arbitrary.

■) Polystyrene vi) Styrene copolymer N,t c) Styrene-acrylonitrile copolymer (
AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin-containing styrene-maleic anhydride copolymer CSMA resin), styrene-acrylic ester-
Acrylamide copolymer, styrene-butadiene copolymer (SBR), styrene-vinylidene chloride copolymer,
Styrene-methyl methacrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

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

viii) Coumarone-indene resin A coumaron-indene-styrene homopolymer or copolymer.

1x) 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 R10 CH-C- C-0R2゜1 In the above formula, Rlo represents a hydrogen atom or an argyl group, and R2o represents a substituted or unsubstituted alkyl group. In this case, in the above formula, Rlo is preferably a hydrogen atom and a lower alkyl group having 1 to 4 carbon atoms, particularly 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 R20 is a substituted alkyl group, a substituted alkyl group The group is preferably a hydroxyl group, a halogen atom or an amine 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 containing two or more types of repeating units.

×1) Polyacrylonitrile ×11) Acrylic acid copolymer (e.g., acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer) polymers, acrylonitrile-vinylpyridine copolymers, acrylonitrile-methyl methacrylate copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-butyl acrylate copolymers, etc.

In this case, the copolymerization ratio can be arbitrary.

xiii) Diacetone acrylamide polymer A diacetone acrylamide polymer obtained by fully reacting acrylonitrile with acetone.

×1■) Polyvinyl acetate

The copolymerization ratio may be arbitrary.

XV1) Polyvinyl ethers, such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc.

xviD polyamide In this case, the polyamides include nylon 6, nylon 66, nylon 61o1 nylon 612, nylon 9,
Nylon 11. In addition to regular homonylons such as nylon 12 and nylon 13, nylon 6/66/610. Copolymers such as nylon 6/66/12, nylon 6/66/11, or modified nylon may also be used.

xviii) Polyesters For example, various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, r-dipic acid, and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, and ethylene. Condensates and co-condensates with glycols such as glycol, tetramethylene glycol and hexastyrene glycol are suitable. Among these, condensates of aliphatic dibasic acids and glycols and co-condensates of glycols and aliphatic dibasic acids are particularly
Particularly suitable.

Furthermore, for example, a modified glycital resin, which is a condensation product of phthalic anhydride and glycerin, is esterified and modified with a fatty acid, a natural resin, etc., and the like can also be suitably used.

xix) Polyvinyl acetal resin Polyvinyl alcohol, polyvinyl formal obtained by acetalization, and four polyvinyl acetal resins are all suitably used.

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

XX>Polyurethane resin A polyurethane resin obtained by condensation of glycols and diisocyanates, particularly a polyurethane resin obtained by condensation of alkylene glycol and alkylene diisocyanate, is suitable for the thermoplastic polyurethane resin IVj having a urethane bond.

xx1) Polyether styrene formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polyzolopylene oxide and glycol, zolobylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc.

xxii) Cellulose derivatives Organic acid esters, ethers or mixtures thereof.

xxiii) polycarbonates such as polydioxydiphenylmethane carbonate,
Various polycarbonates such as polydioxydiphenylethane carbonate and dioxydiphenylpropane carbonate.

A blend of two or more of the above i) to yxiii) of XX.

Blend with Mataha and other thermoplastic resins.

Note that the self-oxidizing property and the molecular weight of the thermoplastic resin may vary.

The self-oxidizing or thermoplastic resin and the dye are usually layered at a weight ratio of 1:0.1 to 100.

Furthermore, it is preferable that the recording layer contains oxygen inchar. This greatly reduces deterioration of the medium due to long wavelength light.

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, the central metals include Ni, Co, Cu
, Mn, etc. are preferred, and the following compounds are particularly preferred.

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 (II) Acetylacetonate Q2 C
u(I) acetylacetonate Q3 Mn(1)'
γ acetylacetonate 4 Co(II) acetylacetonate 2) Bisdithio-α-diketone system (1) (4) Here, R-R represents an alkyl group or an aryl group, and M is a 27-valent transition metal. represents an atom.

Q5 N1 (It) dithiobenzyl Q6 N1 (II) dithiobiacetyl 3) bisphenyldithiol system Here, R+51 and R (6) are an alkyl group such as a methyl group, or a halogen atom such as c, e, etc. where M represents a divalent transition metal atom such as Ni.

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-100s (same as above) Q13 PA, -1006 (same as above) 4) Salicyl Aldehyde oxime system where R(7) and R(8) represent an alkyl group, and M represents a divalent transition metal atom.

Q14 N1(II)0- (N-isopropylformimidoyl)phenol Q15 N1(Il)0- (N-dodecylformimidoyl)phenol Q16 Co(Il)O-(N-dodecylformimidoyl)phenol Q17 Cu (I[)O-(N-dodecylpho/l/muimidoyl)phenol Q18 N1(n)2, 2'-(trilomethylidine in ethylene bis)]-diphenol Q19 Co(■)2, 2'-(in ethylene bis Trilomethylidine)]-diphenol Q20 N1(I[)2,2'-(1,8-nafburene bis trilomethylidine)]-diphenol Q21
N1(n)-(N-phenylformimidoylsiphenol Q22 Co(II)-(N-phenylformimidoylsiphenol Q23 Cu(II)-(N-phenylformimidoylsiphenol Q24) N1(1) Salicylaldehyde phenylhydrazone Q25 N1 (If) Salicylaldehyde Oquine 5)
Thiobisferrate chelate system R (1) where M is the same as above, Rt91 and R (1
0) represents a γ-alkyl group, and R(4) represents an r-mino group.

Q26 NX(1) n-butylamino(2,2'-thiobis(4-tert-octyl)-ferulate J Q27 N1(n) n-butylamino(2,2'-thiobis(4-tert-octyl) -Felt] Such an oxygen-encharging material is synthesized according to a known method.

The amount of the heavy ring oxygen quencher is generally 0.05 to 12 mol, particularly 0.1 to 12 mol, per mol of the penetrating dye.
It is contained in an amount of about 1.2 mol.

In order to form such a recording layer, it is generally necessary to apply the coating according to a conventional method, and the thickness thereof is generally 0.03 to 2 μm.
It is considered to be a degree. Alternatively, when the entire recording layer is formed using a dye alone, vapor deposition, sputtering, 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, and the like.

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 systems such as toluene and xylene, and halogenated alkyl systems 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.

In addition, the base body may contain 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 surface when using a transparent substrate, various uppermost protective layers, etc.
It is also possible to provide a single layer or the like.

However, since the dye of the present invention itself has extremely high reflectance, it is usually not necessary to use such a base or upper reflective layer.

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 surface are used, and the recording layers are placed facing each other, and the substrates are held facing each other for a predetermined period of time, and the substrate is sealed to prevent dust and scratches. It can also be used as a Kaname.

(2) Specific Effects of the Invention The medium of the present invention is irradiated with recording light in pulses while running or rotating. At this time, the self-oxidizing compound is decomposed due to the heat generated by the dye in the recording layer, or
Thermoplastic resin and pigment are catalyzed and bits are formed.

In this case, especially when using tri- or tetracarbocyanine dyes, +11.750.780.83.0 n
When using a recording semiconductor laser, a diode, etc. with a wavelength of m, extremely good writing can be performed.

The bits 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.

In addition, as recording or reading light, He-Ne
A laser or the like can also be used.

(2) Specific Effects of the Invention According to the present invention, writing with extremely high sensitivity and reading with an extremely high S/N ratio can be performed using sound having a wavelength of 750 to 830 nm.

In this case, the raw and archival properties are extremely high.

In addition, it is possible to form pits with an extremely good shape, and since the reflectance is extremely high compared to other tri- or tetracarbocyanine or Ni, Pt dithiol complexes, the readout C/N ratio is also extremely high.

And, when containing all -1 term oxygen quenchers,
Even when held in the presence of infrared light, the singlet oxygen generated by energy transfer from the excited state of the carbocyanine dye is effectively converted to the triplet state by the quencher. Deterioration is extremely low, and raw preservation and archival preservation properties are greatly improved.

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

Furthermore, it has high stability against heat and good shelf life.
There is little deterioration in writing characteristics.

Further, there is little deterioration in characteristics even when erasing and rewriting is performed.

(2) Specific Examples of the Invention The present invention will be explained in more detail below with reference to specific examples of the invention.

Implementation F! /III 1 Using the dyestuff shown in Table 1 below, resin R1 - heavy ring oxygen quencher Q, it was dissolved in a predetermined solvent at the ratio shown in Table 1, and placed on an acrylic disk substrate with a diameter of 15 Crn. Various media were obtained by coating to a thickness of 0.2 μm.

In this case, in Table 1, NC is nitrogen content 11.5
~12.2 inches, viscosity based on JIS K6703 [20 seconds of nitrocellulose teal.

In addition, CI is coumaron-indene resin (manufactured by 1 Tetsu Kagaku Co., Ltd. V-120, number average molecular weight 730), NY is 6,6-nylon (number average molecular weight 30,000), and PS is polystyrene (number average molecular weight 30,000). ) respectively.

Furthermore, the dye used was from the shop shown above, and the comparative dye A was 010, and R1°R1 was -CH
:+, comparative color, $B is near-infrared absorbing dye PAI 006 shown as Quencher-Q13
(manufactured by Mitsui Toatsu Chemical Co., Ltd.), and as comparative dye C, a tricarbocyanine dye having a ring f in benzo f7zo having the following structure was used.

In addition, the quencher used is shown in the cup as 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, set this to 180
While rotating with Orpm, l'J) GaAs -Ga
As semiconductor laser recording light (830nm) total 1μm
It was irradiated in the form of a pulse train at a predetermined frequency and a condensing part output lOmV) to condense the light to φ.

Each medium was irradiated with write light with a different pulse width, and the pulse width at which an extinction ratio of 2.5 was obtained was measured, and the reciprocal of the pulse width was taken as the write sensitivity. The results are shown in Table 1.

In this case, the extinction ratio is the degree of attenuation in the bit portion of the reflectance of the medium surface of readout light, which will be described later.

Separately, writing was performed with a pulse width of '11OOnsec.

After this, 1 mW semiconductor laser (830 nm) readout light? The initial C/N ratio between peaks on the disk surface and the C/N ratio after 5 minutes of irradiation were measured by irradiation as a pulse of 1 μsec width and 3 KHz.

Furthermore, separately, the medium after writing was stored in the dark under the conditions of 60°C and 90% relative humidity for 5000 hours, and the C/N ratio after storage was determined as follows: Measured using an optical microscope. 0 means not present at all;
△ indicates less than 10, and X indicates dog than 10.

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

The results are shown in Table 1.

From the results shown in Table 1, the effect of the present invention is clear in the comparison between the medium of the present invention and the comparative medium.

Example 2 Using mediums A 24 to 29 of Example 1, writing was performed in the same manner as in Example I, and then erasing was performed by heating the medium at 150° C. for 115 seconds using an infrared heater.
It has been confirmed that each medium can be successfully erased and rewritten many times.
June 23rd, Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office1, Indication of 4G Patent Application No. 177776 of 1982, Name of invention Optical Recording Medium3, Relationship with Nagisa 11 cases to be amended Patent Applicant Appointment Office
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) TDC Co., Ltd. Representative Nagisa
Kan Okura 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
Goyabe Building, 1st Floor Telephone: 988-16806 The statements in columns i'3 and Detailed Description of the Invention j of the Statement of Contents of the Amendment are amended as follows.

■) In the 17th line of the 2nd page, ffNi, Co, Cu.

M n j is INi , Co , Cu , M
n.

Pd and PLj are supplemented.

“1) Acetylacetonatogyrate QINi (I
I) Acetylacetonate Q2Cu(II) Acetylacetonate Q3 Mn(III) Acetylacetonate Q4Co(II) Acetylacetonate 2) Bisdithio-α-diketone system where R(1LR(4) is substituted or unsubstituted represents an alkyl group or an aryl group, M is Ni, Co
, represents a transition metal atom such as Cu, Pd, or Pt.

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

Q5Ni(IT) dithiobenzyl Q6Ni(II) dithiobiacetyl 7 N”(C4H9)4 3) Bisphenyldithiol system Here, R(5) and R(8) are an alkyl group such as a methyl group, or C1 etc. represents a halogen atom, etc., and M is Ni, Co.

Represents a transition metal atom such as Cu, Pd, or Pt. Furthermore, -a and b are each 0 or an integer of 4 or less.

In addition, M in the above structure has one charge, and is a cation and 1!
2 may be formed, and further, other ligands may be bonded above and below M.

Examples of this include the following:

QIOPA-1001 (Product name: Mitsui Toatsu Fine Co., Ltd.) Qll PA, -1002 (Product name: Mitsui Toatsu Fine Co., Ltd.)
Ni-bis(toluenedithiol)tetra(t-butyl)ammonium] Q12 PA-1003 (same as above) Q13 PA-1005C same as above Ni-bis(dichlorobenzene)tetra(7-butyl)ammonium] Q14 PA -tooe (Same as above Ni-bis(trichlorobenzenedithiol) tetra(thi-butyl)ammonium) Q15. Go-bis(benzene-1,2-dithiol)
Tetrabutylammonium Q16 Co-bis(O-xylene-4,5-dithiol)tetra(t-butyl) Ammonium Q17 Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18N+-bis(O-xylene-4 ,5-dithiol)tetrabutylammoniumQ19Ni-bis(5-rioobenzene-1,2-dithiol)tetrabutylammoniumQ2ONi-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetrabutyl Ammonium Q21Ni-bis(3,4,5,6-titrachlorobenzene-l,2dithiol)tetrabutylammonium 4) Salicylaldehyde oxime system (?) (8) Here, R and R represent an alkyl group, and M are Ni, Co, Cu.

Represents a transition metal atom such as Pd or Pt.

Q24 Ni (II) o-(N-isopropylformimidoyl)phenol Q23 Ni (II)o -(N-dodecylformimidoyl)phenol Q24 Co (II)o -(N-dodecylformimidoyl)phenol Q25 Cu (II) o -(N-dodecylformimidoyl)phenol Q26 Ni (n)2.2'-(: nitrilomethylidine on ethylene bis)]-diphenol Q27 Co (II)2.2'-( Ethylene bis(
Nitrilomethylidine)]-diphenol Q28 Ni (II) 2.2'-C1
, 8-naphthylenebis and nitrilomethylidine)]-diphenol Q29 Ni (II)-(N-phenylformimidoyl)phenol Q30 Co (II)-(N-phenylformimitoyl)phenol Q31 Cu(II) =(N-phenylformimidoyl)phenol Q32 N1(II) salicylaldehyde phenylhytrason Q33 N1(II) salicylaldehyde oxime 5) Thiobisferrate chelate system R(9) R(1
0) (9) Here, M is the same as above, R, and R (10)
represents an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q34 Ni (II) n-butylamino [2゜2
'-Thiobis(4-tert-octyl]-felt) (Cyasorb-LTV-1084 (American Cyanamid Co., Ltd.)) Q3
5 Co(II) n-butylamino[2゜2'-thiobis(4-tert-octyl)-ferulate] Q36 Ni(II)-2,2'-thiobis(4
-tert-octyl)-ferrate ■) On page 39, line 13, ffQ13j is replaced with l'Q14
Correct it as j.

■) In Table 1 on pages 42-43, [
'Q13j to 1rQ14. fl, TQl 4j]'
Correct Q22j, lrQ, and 25j to IQ33j.

Claims (1)

[Scope of Claims] 1. An optical recording medium comprising a recording layer containing a light-absorbing dye represented by the following formula CI) on a substrate. Formula (1) (In the above formula [1], Q and Q' are respectively,
represents a fused aromatic ring, R1 and present each represent a substituted or unsubstituted alkyl group having 4 or more carbon atoms, R21R;
3 and ~ each represent an alkyl group or an aryl group, L represents a linking group forming a carbocyanine, X- represents an anion, and m is O or I. ) The number of carbon atoms of 2R1 and R1 is 4 to 19, respectively.
An optical recording medium according to claim 1. 3. A light-absorbing dye represented by the following formula 1) on the substrate,
An optical recording medium characterized by having a recording layer made of a resin. Formula (I) (In the above formula (1), Q and Q' are each,
Represents a fused aromatic ring, R1I? and R; each represents a substituted or unsubstituted alkyl group having 4 or more carbon atoms, R2, R;
R3 and R2 each represent an alkyl group or an aryl group, L represents a linking group forming a carbocyanine, X- represents an anion, and m is O or 1. ) 4, R1 and R: each have 4 to 1 carbon atoms.
9. The optical recording medium according to claim 3, which is No. 9. 5. On the substrate, a light-absorbing dye represented by the following formula CI),
- an optical recording medium having a recording layer containing a heavyt oxygen quencher. (In the above formula (1), Q and Q' are each
represents a fused aromatic ring, R1 and R, r each represent a substituted or unsubstituted alkyl group having 4 or more carbon atoms, R21R'21
R3 and R'3 each represent an alkyl group or an aryl group, L represents a linking group for forming a carbonanine, X- represents an anion, and m is 0 and 1. ) 6. The number of carbon atoms in Tokisui and R; is 4 to 19, respectively.
The optical recording medium according to claim 5. 7 On the substrate, a light-absorbing dye represented by the following formula (1),
An optical recording medium comprising a recording layer containing a resin and a doublet oxygen quencher. Formula (1) (In the above formula (1), Q and Q' are respectively,
represents a fused aromatic ring, R1 and R: each represent a substituted or unsubstituted alkyl group having 4 or more carbon atoms, and R2+ R'2.
R3 and R2 are each an alkyl group or /”
IJ- represents a group; L represents a linking group for forming a carbocyanine; X- represents an anion; m is 0 or 1; ) 8, the number of carbon atoms of Ro and R: is 4 to 1, respectively
9. The optical recording medium according to claim 7, which is No. 9.