JPS6073893A - Optical recording medium - Google Patents

Abstract

PURPOSE:To prevent regenerative deterioration caused by reading light, in a heat mode optical recording medium, by containing a quencher in a composition of a dye being a color reaction product of a specific compound and an acidic material. CONSTITUTION:The dye in the recording layer on a base material comprises a color reaction product of a compound represented by formula and a quencher is contained in a composition of said dye. This quencher is pref. a transition metal chelate compound. By this method, regenerative deterioration caused by reading light is reduced, light fastness is enhanced and the deterioration in characteristics during preservation in a light room is extremely reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION ■ BACKGROUND OF THE INVENTION Technical Field The present invention relates to an optical recording medium (11), 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 there is no contact between the recording head and the recording head, and for this reason, various efforts are being made to develop 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.

The optical recording medium of this HEATMO P is an optical recording medium that uses recording light as heat, and as an example, a part of the medium is melted or removed using recording light such as a laser, and a part of the medium is melted or removed to form a pit. There is a bit forming type in which writing is performed by forming small holes, recording information using the pits, and reading out by detecting the bits with read light.

Up until now, most of these pit-forming type media, especially those using semiconductor lasers as light sources that allow miniaturization of devices, have recording layers made of materials mainly composed of Te.

However, in recent years, it has become clear that Te-based materials are harmful, and Yoshi Nao/i! ! Due to the need to reduce the temperature to 11 degrees and the need to reduce manufacturing costs, we changed to Te-based.
An increasing number of proposals and reports are being made about media using h-recording layers made of organic materials containing dyes.

For example, for He-Ne lasers, squarylium dye [JP-A-56-46221, V, B.

Jipson and O.L. Jones, J.Va.
c, Sci, Technol.

18 (1) 105 (1981)) and metal phthalocyanine dyes (JP-A-57-82094, JP-A-57-820)
No. 95).

There is also an example of using a metal phthalocyanine dye for a semi-enveloped laser (Japanese Patent Laid-Open No. 86795/1983).

Are these recording layers made by depositing dyes? 4h It is a membrane and Shimoda, and there is no Te type or Inuzashi due to the media manufacturing.

However, the reflectance of the dye-deposited film to the laser is generally small, and it is difficult to obtain a large S/N ratio with the conventional method currently in use, which obtains the readout signal S''t by changing (reducing) the amount of reflected light depending on the bit. Kade@tai.

Well, if you use a so-called air sandwich structure medium in which a transparent substrate carrying a recording layer is integrated with the recording layers facing each other, and writing and reading are performed through the substrate, you can record without reducing the writing sensitivity. It is possible to print the layers,
It is also advantageous in that the recording density can be increased, but such a long-life recording and reproducing method is also not possible with a dye-deposited film. This has a refractive index of a certain value (1°5 for polymethyl methacrylate) and a somewhat high surface reflectance (4% for polymethyl methacrylate), and is used as the base for the recording layer. This is because, for example, polymethyl methacrylate has a reflectance of about 60% or less, so a recording layer that exhibits only a low reflectance cannot be detected.

In order to improve the readout SA ratio of a recording layer made of a dye-deposited film, a vapor-deposited reflective film such as KT is usually interposed between the substrate and the recording layer.

In this case, the vapor-deposited reflective film is only used to increase the reflectance and improve the 8/N ratio, and the reflective film is exposed due to the formation of pits, resulting in an increase in the reflectance, or in some cases, the reflection Although the film is removed to reduce the reflectance, it goes without saying that recording and reproduction cannot be performed through the substrate.

Similarly, in JP-A No. 5R-IF+1690, I, IR-
132 dye (manufactured by Kodak) and polyvinyl acetate.
Y, Law, et aL, Appt.

Phys, Leti, 39(9)718. (1981)
discloses a medium in which a recording layer made of a dye and a resin is formed by a coating method, such as a recording layer made of 3゜3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate. .

However, these cases also have the same drawback as the dye-deposited film in that a reflective film is required between the substrate and the recording layer, and recording and reproduction cannot be performed from the side of the substrate.

As described above, in order to enable recording and reproduction through a substrate, the organic material itself needs to exhibit a high reflectance.

However, conventionally, there are very few examples of a single layer of organic material exhibiting high reflectance without laminating a reflective layer.

It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits a slightly high reflectance (P, Kiuits, et al.).

The writing sensitivity is low, probably due to the high sublimation temperature.

Furthermore, thiazole-based and quinoline-based cyanine dyes and merocyanine dyes also exhibit high reflectance, and a proposal based on this was made in JP-A-58-112790. Furthermore, it has low solubility in solvents, is easily crystallized, and is extremely unstable against readout light and immediately decolors, making it unsuitable for practical use.

In view of these circumstances, the present inventors have developed a single-layer indoline-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. It is proposed to be used as a membrane (patent application 1983).
-134397, 57-134170).

In addition, even if other cyanine dyes such as indoline, thiazole, norin, selenazole, etc.
It has been proposed that solubility can be improved and crystallization can be prevented by introducing a long-chain alkyl group into the molecular formula (Japanese Patent Application No. 57-182589, Japanese Patent Application No. 57-177776, etc.).

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a quencher to cyanine-wrapped and twisted cyanine in order to prevent deterioration during playback (patent application 1982-
No. 166832, No. 57-168048, etc.).

By the way, as one type of colored thread, it is known that a compound represented by the following general formula CI) reacts with an acidic material (for example, a phenol resin) to produce color (Japanese Patent Publication No. 58-27825,
Special Publication No. 58-27824, etc.).

General formula CI) (In the above general formula (I), one represents a non-gold JA atomic group necessary for forming a 5-, 6-, or 7-membered ring to which the aromatic ring may be fused, B represents a pyrrole ring residue to which a substituted or unsubstituted aminophenyl group or an aromatic ring may be fused; B represents a pyrrole ring residue to which an unsubstituted aminophenyl group or an aromatic ring may be fused; , X represents a substituted or unsubstituted aminophenyl group or a pyrrole ring residue to which an aromatic ring may be fused, and Y and 2 each represent a hydrogen atom or a monovalent group.) Therefore, It is conceivable to construct an optical recording medium using such a dye, and when forming a six-layer recording layer using such a dye, a single layer JM is used without laminating a reflective layer.
'However, it has been confirmed that writing and reading can be performed through the substrate.

However, when reading after writing, the readout light <′
The dye is bleached by the back irradiation, and the readout S/
There is a drawback that the regeneration deterioration resulting in the deterioration of the N ratio is large, making it impractical for practical use.

■ Purpose of the invention The goal is to provide recording media.

Such objects are achieved by the invention described below.

That is, the present invention provides an optical recording medium having a recording layer made of a dye composition on a substrate, wherein the dye composition has the general formula (1).
Colored products produced by the reaction between the compound shown in and acidic materials,
An optical recording medium characterized in that a quencher is contained in a dye composition.

General formula (1) (In the above general formula (I), A represents a nonmetallic atomic group necessary to form a 5-membered, 6-negative or 7-membered ring to which the aromatic ring may be fused, B represents a pyrrole ring residue to which a substituted or unsubstituted aminophenyl group or an aromatic ring may be fused; B represents a pyrrole ring residue to which an unsubstituted aminophenyl group or an aromatic ring may be fused; , X represents a substituted or unsubstituted aminophenyl group or a pyrrole ring residue to which an aromatic ring may be fused, and Y and Z each represent a hydrogen atom or a monovalent group. Specific Configuration The specific configuration of the present invention will be explained in detail below.

In the recording layer of the optical recording medium of the present invention, the above general formula (1) is used.
It contains one or more of the color-forming compounds represented by the formula and a color-forming material that reacts with it.

In the above general formula CI), A represents a nonmetallic atomic group necessary to form a 5-, 6-, or 7-membered filler metal to which an aromatic ring may be condensed, and the following are particularly preferred. .

Al) Respectively substituted (e.g. alkyl, chloro, dichloro, trichloro, tetrachloro, bromo, sifuromo, tovi''lomo, tetrabromo, nitro, A2) Substituted (e.g. nitro) t, C, unsubstituted or B , represents a pyrrole ring residue to which a substituted or unsubstituted aminophenyl group or an aromatic ring may be fused, and the following are particularly preferred.

Here, s R1 and R2 each represent a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, or acyl group, and
For example, it is a hydrogen atom or a monovalent group.

In this case, R1 and R2 may be the same or different, but each is a hydrogen atom or a substituted or unsubstituted alkyl group (methyl, ethyl, furoyl, butyl, pentyl, hexyl, benzyl, etc.) ,
represents a cycloalkyl group (cyclohexyl, methylcyclohexyl, etc.) or an acyl group.

However, it is preferable that both R2 and R2 are not phenyl.

R3 (same as R3-R6 in Σ) represents a hydrogen atom or a group of 111Ill.

In this case, monovalent groups include alkyl, aryl, alkoxy, halogen, aralkyl, dialkylamino,
Monoalkylamino, amino, acylamino, mercapto, alkylthio and the like are preferred.

B'2) R6 R31'L9 Here, R9 and RIO may be the same or different, and each is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group or aryl group (phenyl group). .

Moreover, s R3-R6 may be the same or different from each other, and each has the same meaning as R3 above.

Ordinary 3 Crow R4 Here, 几9 and R1 (l are the same as above.

Moreover, R3-R8 may be the same or different from each other, and each has the same meaning as R3.

Item j■ represents B and his group [preferably B1] to B3].

X In this case, it is preferable that the ratio is 10=0-Y.

Here, X may be a substituted or unsubstituted aminophenyl group or a pyrrole ring which may be bonded to 1, respectively, but the following are particularly preferred.

XI) ■Mo31L4 Here, 兠 and 几2 are i? R3-R6 may be the same or different, but are the same as R3 above.

X2) 9 Here, R9 and RIG may be the same or different, and each is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group or phenyl group.

X3) 9 Here, the box 9 is the same as above.

X4) X5) R6 B,, R3 Here, 几3 to R6, R9', and 1410 are the same as above.

X6) ■X7) Y and Z may be the same or different, and each represents an aquatic atom or a monovalent group.

In this case, monovalent groups include norogen, alkyl,
Examples include carbalkoxy, benzyl, substituted or unsubstituted phenyl, pyridino, and the above X.

(1) When X is XI), X2), X3) or X5), Y is XI), X2>, X3) or X4), or hydrogen or carbalkoxy, 2 is hydrogen, halogen, alkyl, carboalkoxy,
Preference is given to benzyl, substituted or unsubstituted phenyl or pyridino.

(2) When X is X4), X6), or X7), Y and Z are hydrogen, halogen, alkyl,
Preference is given to carbalkoxy, benzyl, iil or unsubstituted phenyl or pyridino.

Such a compound represented by the above general formula [1] is synthesized, for example, according to Japanese Patent Publication Nos. 58-27825 and 58-27824.

Next, specific examples of the compound represented by the formula [I] are shown below.
Ru.

A B ′ C3 4 at at at at at -0H=OHDN(OH3)2 t at O,H5 r 02H5 Q 2kl 5 1 021 (5 H20 1 These general formulas CI) Reaction of compound t with acidic material Forms a colored substance and functions as a pigment.

In this case, the acidic material is any compound within the definition of a Lewis acid, ie an electron acceptor. Preferably, an acidic organic polymer, such as a phenolic polymer, is used as the acidic material.

Acidic polymeric materials useful in the present invention include phenolic polymers, phenolic acetylene polymers, alkylphenolacetylene polymers, maleic rosin resins, partially or fully hydrolyzed styrene-maleic anhydride copolymers, and ethylene-anhydrous Suitable examples include maleic acid copolymers, carboxypolymethylene, wholly or partially hydrolyzed vinyl methyl ether-maleic anhydride buty copolymers, and mixtures thereof.

These acidic materials and the color-forming compound represented by the general formula CI) are reacted in advance in a predetermined solvent, and this reaction product (colored substance) is separated and recorded. It may also be added to the layer coating composition.

In this case, suitable solvents include toluene, xylene, petroleum distillates, perchlorethylene, etc., as well as dioctyl adipate, biphenyl, diphenylalkane, and the like.

Or paint! It is also possible to obtain a reactive colored product in the composition liquid by adding predetermined amounts of a color-forming compound and an acidic material to the am composition liquid.

In such cases, it is common to use an excess of an acidic material, particularly an acidic organic polymer, to function as a pinter.

In addition, other dyes may be contained together with such a reactive coloring material.

The recording layer may also contain various other resins.

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

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

1) Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc.

11] Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene -maleic anhydride copolymer,
such as ethylene propylene terpolymer (EPT).

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

1ii) 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 with vinyl chloride graft polymerized, etc.

In this case, the copolymerization ratio can be arbitrary.

i) Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

V) Polystyrene polymer 1) Styrene copolymer For example, styrene-acrylonide 9 copolymer (AS4
1Il fat], styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-acrylic acid 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.

vii) Styrenic type polymers such as α-methylstyrene, P-methylstyrene, 2
, 5-dichlorostyrene, α.

β-vinylnaphthalene, α-vinyl bilysine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as (f, a copolymer of α-methylstyrene and methacrylate ester).

viii) Coumarone-indene resin Coumarone-indene-styrene copolymer.

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

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

Formula R10 CH-C- -0R20 1 In the above formula, R1 represents a hydrogen atom or an alkyl group, and R20 represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R10 is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group).

Further, R2O may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when Rho is a substituted alkyl group, the alkyl group is The substituent to be substituted 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 having two or more repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer, for example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer , acrylonitrile-methyl methacrylate copolymer,
Acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary! I can do that.

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

xiv) Polyvinyl acetate xv) Vinyl acetate copolymers, such as copolymers with acrylic esters, vinyl ethers, ethylene, vinyl chloride, etc.

The copolymerization ratio may be arbitrary.

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

xvii) Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-10. In addition to regular homonylons such as nylon 6-12, nylon 9, nylon 11, nylon 12, and nylon 13, nylon 6/6-6/6-1
0, nylon 6/6-6/12, nylon 676-6/
Polymers such as No. 11 or modified nylon may be used as the case may be.

Σviii) Polyester For example, various dibasic acids such as aliphatic dibasic acids such as succinic acid, maleic acid, adipic acid, and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, and ethylene glycol. Condensates and co-condensates with glycols such as , 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, for example, a modified gliptal 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 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 with urethane bonds.

Particularly suitable are polyurethane resins obtained by condensation of glycols and diisocyanates, particularly polyurethane resins obtained by condensation of alkylene glycol and alkylene diisocyanate.

xzi) 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.

xxii) Cellulose derivatives For example, various esters and ethers of cellulose, such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, and mixtures thereof.

xx i i i) Polycarbonates such as polydioxydiphenylmethane carbonate,
Various polycarbonates such as dioxydiphenylpropane carbonate.

xxii) Ionomer Na such as methacrylic acid and acrylic acid.

Li, Zn, Mg salts, etc.

xxv) Ketone resins, for example, condensates of cyclic ketones such as cyclohexanone and acetophenone and formaldehyde.

xxvi) Xylene resin, for example, a condensate of m-xylene or mesitylene with formalin, or a modified product thereof.

xxvii) Petroleum resins C5 type, C9 type, C5-cq, copolymer type, dicyclopentadiene type, or copolymers or modified products thereof.

xxviii) A blend of two or more of the above i) to XX), or a blend with other thermoplastic resins.

Note that the molecular weight, etc. of self-oxidizing, thermoplastic, etc. resins may vary.

The weight ratio of such resin and the above-mentioned dye is usually 1.
The layers are deposited in a wide range of ratios from 0.1 to 100.

Such a recording layer contains a quencher.

As a result, the S/
Reproduction deterioration of N ratio is reduced. In addition, light resistance is improved by storage in a bright room.

Various quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with the dye-binding resin. In this case, the central metal is preferably Ni, Co, Cu, Mn, Pd, Pt, etc., and the following compounds are particularly preferred.

1) Acetylacetonate chelate Ql-I Ni([)acetylacetonate Ql-2o
u(II) Acetylacetonato Ql-3Mn[l) Acetylacetonate Ql-40ofll) Acetylacetonate 2) Bisdithio-a-diketo represented by the following formula, where kL(1) to R(4) are substituted Represents a non-tanned alkyl group or aryl group, M'/U, Ni
, Oo, Ou, Pd, PL, etc. transition basin atoms 'ti:
WK)

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

In addition, in the following description, phi:t phenyl group, φ
represents a 1,4-phenylene group, φ'Ul, a 2-phenylene group, and benz represents that different groups on the ring bond to each other to form a condensed benzene ring.

3) In the bisphenyldithiol system represented by the following formula, R (5) and R (6) are aqueous l or methyl
, alkyl atoms such as ethyl group, halogen atoms such as at, or amine groups such as dimethylamino group and diethylamino group, etc., IVi, Yu, Ni, Co, Ou, Pd, Pt, etc. Next is the 1% IJjc child refund transfer.

゛Also, with the MVi-weight t of the above structure, a salt may be formed with a υ cation (Oat) such as a quaternary ammonium ion, and other ligands are bonded above and below M. You may do so.

Examples of this include the following: No. 1, and what was stated in the patent application dated September 5, 1982.

4) Dithiocarbamic acid chelate system represented by the following formula, where R[9) and fL(10)B alkyl groups are represented. It also represents transition metal atoms such as MUNi, Oo, Ou, Pd, and Pt.

C4-1O4Hg l'Ji 5) Compound represented by the following formula, where M represents a pheasant metal atom, IVI Q O
u- C5-I Ni Q122CHHa31”l”(Of(
3) 3Q52 1'Ji Q122 (04H9) 4N+
2 C5-3Co Q 2(OtHs)41'JQ5-4
0u Q122i04H9)4N+Q5-5 Pd Q
122fOzl-1s) 4N"Others, '++ Kao 58
-Described in No. 125654.

6) In the compound represented by the following formula, MV′i represents a transition metal atom, 1 , (11) and 几 (122 are ON, 0, respectively)
0 几 , 000FL (14), C0NfL (15) R (
16) or (13) so represents 几(17), R(13) to 几(17) each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and C2 is a 5-membered or 1ri represents the atomic group necessary to form a 6-membered ring, Oat represents a cation, and n u 1 is 7'Cμ2.

'I CI O' 0' 0' 0' In addition, those described in Japanese Patent Application No. 58-127074.

7) Compound represented by the following formula, where M represents a transition metal atom, Oatμ represents a cation, and n is 1 or 2.

and Danshi Q7-I Ni 2 ((n-04Hg)INQ7-2
Ni2[:n-0+6Hax (OHg)aNJ In addition, those described in Japanese Patent Application No. 127075/1982.

8) Bisphenylthiol Q8-I Ni-his(octylphenyl) sulfide 9) Thiocatechol chelate represented by the following formula, where 1
M represents a transition metal atom such as Ni, Co, O, Pd, or Pt.

Further, M'/d- may have a charge t to form a salt with a cation (Oat), and the benzene ring may be substituted with M.

Yu Danmi Q9-I Ni N'' (C4H9)410) Compound represented by the following formula Here, 几 (18) represents a monovalent group, tVi, O
~6, MVi represents a transition metal atom, and Oat U represents a cation.

QIO-I Ni HON(n-0<l(*)tQ10
2 Ni 0113 I N(n-04Hg)n In addition, those described in Japanese Patent Application No. 1983-1983-43-3x.

11) Compounds represented by both the following formulas, especially in the above general formulas [I] and [■], □(201, R(21) , B (22) and (
23) each represents a hydrogen atom or a monovalent group,
R, R, R and R (27) are water (24) (25) (26) elementary atoms -! 1 represents a monovalent crystal, but 几 (button and R, □
and Pus26), □ (26) and R1 (27) are (25)
(25) They may be combined with each other to form a 6-membered ring.

゛Also, M represents a transition metal atom.

21　’　2　2 -N In addition, those described in Japanese Patent Application No. 58-145294.

12) Compound 18 represented by the following formula, where M represents Pt, Ni'): 1jPd,
X+ lX21X31X4 'ri, respectively, 0!1
'TakeS is displayed.

M

13) Compound represented by the following formula, where 几131) is a substituted or unsubstituted alkyl group or aryl group, □(32), , , (33) , R(34) and kL
In (35), the hydrogen atom 1fc represents a monovalent group, but 几 (32) and □ (33), kL (33) and □ (34)
, □(34) and □(35) , well, they combine with each other to form 6
It may also form a membered ring.

Also, s　M't'i　s-represents a transition metal atom.

to) d) to) d) q13=i n0411g HHHHN1Q13”'2
06H6HH (4H5HN1Q13-3 HHben
z Ni KoQ et al., as described in Vf Yorisho No. 58-151928.

14) Compounds represented by the following formulas K, fi(41), , (42), , (43)
, Yohi, , (44) each represent a hydrogen atom or a monovalent group, but □ (41) and kL (42),
1 (42), L (43), □ (43) and 几 (44)
may be combined with each other to form a 6-membered ring.

Further, R (45) and (46) represent a hydrogen atom or a monovalent group.

Furthermore, M is a transition metal atom 'f'.

R (41) □ (42) Xun Dan) Self ¥, (45) Appearance Q14-I HHHHH-N1 Q14-2 HHC4H7000HHNi In addition, those described in Japanese Patent Application No. 58-151929.

15) Compounds (51) (52) (53) (54) represented by the following formulas, where
, R., R.

1, (55), □(56), □(57) and □(5
8) Yes. It represents a 111-valent group containing a hydrogen atom, but R(51) and -52), □(52) and □(53)
, , (53) and 几 (54) +' B (55) and (
56) , , , (56) and □ (57) and l, (5
7) and 1. (58) may be bonded to each other to form a 6-membered ring.

B (59) represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.

X'ri...Represents Rogen.

M i"l: represents a transition metal atom.

-2A1 □ 2 9 9 xl　o.

O'a? In addition, I have published my own information in Japanese Patent Application No. 58-153392.

16) Salicylaldehyde oxime FL (60) represented by the following formula, where R (60) b- and (61) represent an alkyl group, and M is N r + O o + O u
+ P d * P represents a transition metal atom such as.

Q16-1 i -03H7 i -03H7 NiQ
16”'2 (OH2)BOI-43 (OH2)11
0H3 NiQ16-3 (OHz)ttOHa (O
Hz)ttOHa Q.

Q16-4 (OH2)110H3 (OH2)11'
OH3 0uQ 16 - 5 06 H5 06 H
5 N iQ 16 - 6 06 Ha 06 H5
0.

Q 16 - 7 06 H5 06 H6 0 uQ
16-8 NH(4H5 NHO11H5 NiQ16
-9 0H O[(Ni 17) Thiobisferrate chelate system represented by the following formula, where M is the same as above, R(65) and R(
66) represents an alkyl group. Ma7hiM has a single unit and may form a cation (Oat) and a salt.

Q17-2 t-OBH 凰7 0o NHB (04H
o) Q17-3 t -(4HB Ni -18) Phosphonous acid chelate group represented by the following formula? f:. Table j squirrel.

几(71) , , , (72) Kasa Q18-1 3-t-04H, , 5-t-04Hg
,6-OHNi19) Compounds represented by the following formula include 几(81)1. , (82), 几 (83) and 几 (84 藉, representing a hydrogen atom or a monovalent group, 1, , (81), (82), 1 (82) and -83),
□(83) and (84) R may be bonded to each other to form a 6-membered ring f:.

R and 几(88) each represent a hydrogen atom (85) or Vi, a substituted or unsubstituted alkyl group, or an aryl group.

R(86) represents a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group or aryl group.

R (87) represents a substituted or unsubstituted alkyl group or aryl group.

Z is a non-gold necessary to form a 5-membered or 6-membered ring!
A represents the atomic group.

M represents a transition metal atom.

Between ZZ≧ nj, I + H In addition, those described in Japanese Patent Application No. 58-153393.

20) Compounds represented by the following formula, where ■, (91) and 几(92) lri, each hydrogen atom, substituted or unsubstituted alkyl group, aryl group, acyl group, N-alkylcarpamoy/L/%
, N-arylcarbamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, alkoxycarbonyl group or aryloxycarbonyl group, and M represents a transition metal atom 'f:.

几(91) 1(92) L Q20-1 n 04 Hg, OHB N iQ2
0-1 0Hs OHm0-φ-NHOONiOthers,
What is described in Japanese Patent Application No. 155359/1983.

In addition, other quenchers include the following:

21) Benzoate Q21-1 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Geigy)] 22) Hindered amine Q22-1 Existing chemical substance 5-3732 (SANtJ
LLS-770 (manufactured by Niss Pharmaceutical Co., Ltd.)] Each of these clinchers has a dye content of 0.01 per mole.
-12%/L, about 0-1 to 1.2 mol is contained in the poem.

Note that the maximum absorption wavelength of the quencher is preferably greater than or equal to the maximum absorption wavelength of the dye used.

As a result, regeneration deterioration becomes extremely small.

In this case, the difference between the two is preferably 0 or 350 nm or less.

In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method.

The thickness of the recording layer is usually 0.03 to 10 AL.
It is said to be about m.

In addition, such a recording layer may contain other dyes, other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and antioxidants. , and may contain a crosslinking agent or the like.

In order to form such a recording layer, it is usually enough to coat the substrate with a predetermined solvent and dry it.

In this case, the compound represented by the general formula CI), the acidic material, the quencher, and if necessary, the resin may be dissolved in a predetermined solvent to prepare a coating solution.
A reactive colored product is generated in the coating solution or after the coating film is formed.

Alternatively, as described above, by forming a reactive colored substance in advance,
This can also be added to the coating solution.

Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl imbutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, and ethers such as methylseronlube and ethylcellosolf. or aromatic systems such as toluene and xylene.

Alkyl halides such as dichloroethane, alcohols, etc. may be used.

There is no particular restriction on the material of the substrate on which such a recording layer is formed, and it may be made of any of various resins, glasses, ceramics, metals, etc., but materials that are substantially transparent to writing light and reading light may be used. Or preferable.

Further, its shape may be a tape, a drum, a belt, etc. depending on the intended use.

Note that the base body usually has a groove for tracking.

Further, as the resin material for the substrate, a substrate without grooves, such as polymethyl methacrylate, acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyether sulfone, methylpentene polymer, etc., is suitable.

These substrates can also be coated with a primer to improve solvent resistance, wettability, surface tension, thermal conductivity, and the like.

As the primer, for example, titanium-based, silane-based, aluminum-based cambling agents, various photosensitive resins, etc. can be used.

In addition, on the recording layer, various numbers of protective layers,
It is also possible to provide a single layer of half-mirror. however,
It is preferable that the recording layer is a single layer film and that one reflective layer is not laminated above or below the recording 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 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 in pulses while running or rotating. At this time, the dye, which is a reactive coloring substance in the recording layer, melts due to heat generation, and pits are formed.

The pits formed in this manner are read out by detecting the reflected or transmitted light of the readout light, especially the reflected light, while the medium is running or rotating.

In this case, recording and reading may be performed from the substrate side or from the recording layer side, but it is preferable to perform the recording and reading through the substrate.

It is also possible to erase the pits once formed in the recording layer with light or heat and rewrite.

Note that a semiconductor laser, a He-Ne laser, an Ar1z-Chi1He-Cd laser, etc. can be used as the recording or reading light.

(2) Specific Effects of the Invention According to the present invention, reproduction deterioration caused by read light is extremely reduced.

In addition, the light resistance has been significantly improved, and there is extremely little deterioration in characteristics due to storage in a bright room.

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

Furthermore, writing and reading can be performed through the substrate without laminating a reflective layer.

It also has good solubility and little crystallization.

(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 Color-forming compound C1 shown in Table 1 below, acidic material A, and quencher Q were dissolved in a predetermined solvent in the proportions shown in Table 1, and placed on an acrylic disk substrate with a diameter of 30 cm. , 0.07 #L, m thickness was applied to obtain various media.

In this case, in Table 1, A1 is an 80% hydrolyzed styrene-maleic anhydride (1:1) copolymer.

A2 is a 50% hydrolyzed vinyl methyl ether-anhydrous maleic buty copolymer.

Furthermore, the color-forming compounds used were the positive,
I used the later one.

In addition, the quenchers used are indicated by the positive symbol of those exemplified above.

Table 1 also lists the A/C weight ratio and the Q/C weight ratio.

For each medium created in this way, a 1 mW semiconductor laser (830 nm) readout light was applied for 1 psec width.
After irradiation with a 3'KHz pulse for 5 minutes in a stationary state, the change (%) in reflectance from the back side of the substrate was measured.

These results are shown in Table 1.

From the results shown in Table 1, the effects of the present invention are clear.

Example 2 After writing in the same manner as in Example 1 using the media of Example 1, numbers 2 to 6, erasing was performed by heating the medium at 150°C for 15 seconds using an infrared heater. It was confirmed that each medium could be successfully erased and rewritten many times.

Applicant TDC Co., Ltd. Agent Patent attorney Yo Ishii - Continued from page 10 Inventor Takahashi - Husband Type 1 company, Chuo-ku, Tokyo Inventor Akihiko Kuroiwa Type 1, Chuo-ku, Tokyo Inside the company

Claims (1)

[Claims] 1. An optical recording medium having a recording layer formed of a dye composition on a substrate, wherein the dye is a colored product formed by the reaction between a compound represented by the following general formula [■] and a sea-based material. quencher in the pigment composition.
An optical recording medium characterized by containing. General formula CI) (In the above general formula [I], A represents a nonmetallic atomic group necessary for forming a 5-, 6-, or 7-membered ring to which the aromatic ring may be fused. , B represents a pyrrole ring residue to which a substituted or unsubstituted aminophenyl group or an aromatic ring may be fused; B represents a pyrrole ring residue to which an unsubstituted aminophenyl group or an aromatic ring may be fused , X represents a substituted or unsubstituted aminophenyl group or a pyrrole ring residue to which an aromatic ring may be fused, Y and 2 each represent a hydrogen atom (t2: a monovalent group); 2. The optical recording medium according to claim 1, wherein the dye composition contains a resin. 3. The optical recording medium according to claim 1, wherein the quencher is a transition metal chelate compound. The optical recording medium as set forth in item 6. 4J The optical recording medium as set forth in line 1f in which a reflective layer is not laminated on the recording layer - 11 in any one of claims 1 to 3. 5. An optical recording medium according to any one of claims 1 to 4, on which writing and reading are performed.