JPS6096491A - Optical recording medium - Google Patents

Abstract

PURPOSE:To facilitate forming of a tracking groove on the surface and to obtain an optical recording medium of heat modes with easy control of tracking by using a basic material formed by hardening, with activating radiation ray, a compound or composition which can be hardened with activating radiation ray. CONSTITUTION:There are various kinds of compounds that can be hardened by activating radiation ray, for examples, those that produce radicals and etc. by activating radiation ray and have polymerization or cross-linking unsaturated double bonds. Electron beam and etc. may be used for activating radiation, however, in order to penetrate the thickness of a basic material the use of ultraviolet ray is desirable. A writing ray is applied from the sides of the recording layer or the basic material as pulsed ray to the optical recording medium of this invention during its running or rotation. At this time by generation of heat from the coloring matters in the recording layer a self-oxidizing resin decomposes or thermoplastic resin or a coloring matter fuses to form pits.

Description

[Detailed description of the invention]

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. There is a pit-forming type in which writing is performed by forming small holes, information is recorded using the pits, and reading is performed by detecting the pits with a readout light. Until now, most of these pit-forming type media, especially those using a semiconductor laser as a light source that can make the device smaller, have a recording layer made of a material mainly composed of Te. However, in recent years, because Te-based materials are harmful, and there is a need to increase sensitivity and reduce manufacturing costs, organic materials, mainly dyes, are being used instead of Te-based materials. There are an increasing number of proposals and reports on media using recording layers. For example, for He-Ne lasers, squarylium dye [JP-A-58-48221, v. B.Jipson and C.R.Jones, J.
Vac, Sci, Tech-nol, 18 (
1) 105 (1981)) and metal phthalocyanine dyes (JP-A-57-82094, JP-A-57-8209)
5) etc. There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Laid-Open No. 88795/1983). All of these have a recording layer formed into a thin film by vapor deposition of a dye, and there is no major difference from the Te type in terms of medium production. However, the reflectance of a dye-deposited film to a laser is generally small, and the current conventional method of obtaining a readout signal by changing (reducing) the amount of reflected light due to pits cannot obtain a large S/N ratio. In addition, if a transparent substrate supporting a recording layer is integrated with the recording layers facing each other in a so-called air sandwich structure medium, and writing and reading are performed through the substrate, the recording layer can be layered without reducing the writing sensitivity. However, such a recording/reproducing method is also not possible with a dye-deposited film. This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate).
In addition, the surface reflectance is relatively high (4%), and the reflectance through the substrate of the recording layer is about 60% or less for polymethyl methacrylate, for example, so it is difficult to detect a recording layer that exhibits only a low reflectance. Because you can't. In order to improve the reading S/N ratio of a recording layer made of a dye-deposited film, a vapor-deposited reflective film such as A-type is usually interposed between the substrate and the recording layer. In this case, the vapor-deposited reflective film is intended to increase the reflectance and improve the S/N ratio, and the reflective film may be exposed due to pit formation and the reflectance may increase, or in some cases, the reflective film may be removed. It removes the reflectance and reduces the reflectance.
Naturally, recording and reproduction cannot be performed through the substrate. Similarly, JP-A-55-181890 Niha, IR-13
A recording layer comprising two dyes (manufactured by Kodak) and polyvinyl acetate; A recording layer composed of 1'-diethyl-2,2'-trivalent lupocyanine iodide and nitrocellulose, as well as K, Y, Law, et al., Appl. Phys, Lett, 39 (9) 718 (18
81) discloses a medium in which a recording layer made of one dye and a resin, such as a recording layer made of 3゜3'-diethyl-12-7cetylthiatetracarpocyanine and polyvinyl acetate, is formed by a coating method. ing. 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 back side of the substrate. In this way, in order to realize a medium with a recording layer made of an organic material, which is capable of recording and reproducing through a solid body and is compatible with a medium having a recording layer made of a Te-based material. , the organic material itself needs to exhibit a large 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, Kivits, etal, Ap
pl, Phys, Part A 26 (2) 1
01 (1!381), Japanese Patent Publication No. 55-137033]
However, the writing sensitivity is low, probably due to the high sublimation temperature. In addition, it has been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes are used (Yamaki et al., 27th
Proceedings of the Japan Society of Applied Physics 1p-P-9 (1980)), and a proposal based on this was published in JP-A-58-11279.
However, these dyes have low solubility in solvents, are easily crystallized, and are extremely unstable against readout light, causing them to immediately decolorize, especially when applied as a coating film. It cannot be put to practical use. In view of these circumstances, the present inventors first developed an indolenine-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 single layer film (patent application filed in 1973).
No. 7-134397, No. 57-134170). Furthermore, in other cyanine dyes such as indolenine, thiazole, quinoline, and selenazole, long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization. (Patent Application No. 57-182589, Patent Application No. 57-177776, etc.)
. Furthermore, it has improved photostability, especially decolorization by readout light (
We proposed adding a quencher to cyanine dyes in order to prevent regeneration and deterioration (Japanese Patent Application No. 57-1).
88832, 57-1ft No. 8048, etc.). By the way, in the case of such coated media, if the recording layer is directly coated on the surface of the transparent resin substrate without being laminated on the reflective layer, the substrate will be damaged by the coating solvent and the reflectance of the recording layer will decrease. This has the disadvantage that the readout S/N ratio cannot be kept high enough. Such a decrease in reflectance becomes extremely large, especially when writing and reading are performed through the substrate. Further, due to the action of the solvent during coating, dyes and the like are dissolved and diffused into the base resin, resulting in a disadvantage that the reflectance decreases over time. Furthermore, 1. With ordinary resin substrates, the heat generated by the recording layer during writing or erasing causes the substrate surface to thermally deform, resulting in a decrease in reflectance. When writing and reading are performed through the recording medium, heat generation at the interface between the substrate and the recording layer increases, which is a very serious drawback. Furthermore, tracking control is required when writing and reading from such media. Conventionally, in order to control tracking, a tracking groove is provided on the recording layer formation surface of the substrate, and the recording layer on the four parts or convex parts of this groove is used as the track part. This is done by detecting whether the track is off track by utilizing differences in optical properties based on differences in film thickness, or differences in optical properties such as reflection and absorption. When forming tracking grooves on the substrate surface in this manner, tracking control becomes difficult in coated media due to the action of the solvent and thermal deformation. In addition, since this tracking groove has a depth of approximately 0/8n (where 0 is the wavelength of the light and n is the refractive index of the substrate),
It has the drawbacks of being difficult to manufacture, requiring strict processing precision, and low mass productivity. That is, the formation of grooves is usually
This is done by pressing a stamper against a resin plate material for the base, but the stamper wears out, which increases the cost and lowers the yield. II. OBJECTS OF THE INVENTION It is an object of the present invention to minimize the decrease in the S/N ratio due to thermal deformation due to heat generation during writing and erasing, minimize the deterioration of the S/N ratio due to solvent during coating of the recording layer, and reduce the deterioration of the S/N ratio due to the It is an object of the present invention to provide an optical recording medium having a substrate in which tracking grooves can be formed easily and with high productivity, and tracking can be easily controlled. Such objects are achieved by the invention described below. That is, the present invention has a substrate formed by curing and molding a compound or a composition thereof that can be cured by actinic radiation,
This optical recording medium is characterized by having a recording layer made of one dye or a composition thereof on the surface of this substrate. ■Specific structure of the invention The specific structure of the present invention will be explained in detail below. The substrate used in the present invention is formed by curing and molding a compound curable with actinic radiation or a composition containing this compound with actinic radiation. In this case, the compound that can be cured by actinic radiation can be of various types, such as those having unsaturated double bonds that generate radicals and polymerize or crosslink by actinic radiation. Various known methods are possible. In such a case, the substrate itself requires mechanical strength and dimensional stability as a substrate, and lILm to 4IIm,
Generally, it is molded to a thickness of about 100#LL1-3cm. For this reason, although an electron beam or the like may be used as the active radiation, it is preferable to use ultraviolet rays in order to enable transmission through the thickness of the substrate. The preferred wavelength of ultraviolet rays is 200 to 200 degrees. In this case, examples of UV-curable compounds (polymers, oligomers, polymers) that can be particularly suitably used in the present invention include the following. 1. Monofunctional polymers or oligomers 1.1 Monofunctional polymers such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, benzyl acrylate, Calpitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, N-methylol acrylamide, N-diacetone acrylamide, N, N '-methylenebisacrylamide, styrene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, etc. 1.2 Polyfunctional acrylic monomers or oligomers Examples include ethylene glycol cyacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and polypropylene glycol diacrylate. Acrylate, polypropylene glycol dimethacrylate, butylene glycol cyacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol cyacrylate, 1.6-hexane Thiol diacrylate, 1,6-hexane thiol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and the like. 1.3 Allyl polyfunctional degradable monomers such as diallylphthalade, diallylisophtala-1
- Diallyl maleate, diallyl chlorendate, diallyl adipate, diallyl diglycolate, triallyl cyanurate, diethylene glycol bisallyl carbonate, etc. 1.4 Ring-opening polymerization monomers, such as glycidyl cinnamate and epoxy derivatives of oxychalcone. 1.5 Urethane type acrylic ester 1.6 Unsaturated ester of polycarboxylic acid 1.7 Unsaturated amide 1.8 Ester metal salt with inorganic acid 1.9 Monomer with acetylenically unsaturated group 1.10
Monomers with glycisin groups 1.11 Diazonium salts 1,12O-quinone azides, such as sulfonic acid esters of 0-naphthoquinone diazide, etc.1.13 Others, such as dihydroxychalcone, divanillalacetone, divanillarcyclopentanone, etc.1. 14 Vinyl monomers with photosensitive group 1) Cinnamoyl type, e.g. the following 2) Cinnamylidene type, e.g. the following 3) Furyl acryloyl type, e.g. the following 4) Coumarin type, e.g. the following 5) Pyrone type, e.g. the following 6) Pe/zalacetophenone type, for example, the following 7) Anthracene type, for example, the following 8) Stilbene type, for example, the following 9) α-phenylmaleimide type, for example, the following 10) Azide yarn, for example, the following OHI = OHOOH10HzNm 11) Unsaturated systems such as the following OHM =OH0000H! 0H=OI(10H2=O
HOOIb 0HaU-00-OH=OHz12) Benzophenone series For example, the following OH2=O(OHs)OOUOH20H(OH)OHx
O-00GOUQ13) Benzoin type 1!゛U is the following 14) 1,3-dioxolane type, U is the lower self-15) dithiocarbamate type; 1e is the following 0H2=OI (-8-O8-NR 16) azadioki Bicyclo-based, for example, the following 17) Stilbene-based, for example, the following 2. Polymers or prepolymers Existing polymers, such as those chemically bonded with various photosensitive groups as exemplified by the following photosensitive groups and/or monomers. Examples of the Bolya include various epoxy resins, polyurethane, polyamide, polyacrylic unsaturated polyester, polyvinyl alcohol, silicone resin, maleic acid copolymer, cellulose derivatives, vinyl chloride-vinyl acetate copolymer, resinous polyol acrylic resin, etc. In addition to the above, photosensitive groups include olefin, cinnamoyl, cinnamylideneacetyl, benzalacetophenone (
chalcone), styrylpyridine, α-phenylmaleimide, phenyl azide, sulfonyl azide, carbonyl acid, diazo, 0-quinonediazide (diazo oxide)
, furyl acryloyl, coumarin, pyrone, anthracene, benzophenone, benzoin, stilbene, dithiocarbamate, xantate, 1,2,3-thiadiazole, cyclopropene, aza-dioxabicyclo, and the like. Furthermore, cyclized rubber, polycon (polyurethane obtained by reacting polyether glycol and tolylene diisocyanate, and having allyl isocyanate or allyl alcohol bonded to the terminal end thereof to introduce an allyl group) are also useful. A photosensitive crosslinking agent can be added to compounds such as polymers, oligomers, and 7mers that can be cured by ultraviolet rays.The amount of crosslinking agent added is determined by
) 80 wt% or less, especially about 1 to 80 wt%. There are no particular restrictions on the crosslinking agent to be used, but the following are preferred. 1. Dichromate A mixture of a water-soluble polymer compound such as gelatin, glue, egg white, gum arabic, polyvinyl alcohol, etc. and eastern chromate 2. Organic azide compound such as 4,4'-diazidostilbene, 4.4′ −
3 Sulfur compounds such as diazide chalcone3, sulfur compounds such as pentaerythritol tetrakis (β-mercaptopropionate)4, photodimerizable compounds such as silicic acid, etc.Furthermore, initiators and sensitizers can also be added. The amount of the initiator and sensitizer added is about 0.001-10 wt% of the compound curable by ultraviolet light. Although there are no particular limitations on the initiator and sensitizer used, the following are preferred. 1. Benzoin ethers such as inbutylbenzoin ether, isopropylbenzoin ether, benzoin ethyl ether, benzoin methyl ether, etc. 2. α-Azyloxime esters Examples lf, 1-phenyl-1,2-propanedione-2
-(o-ethoxycarbonyl)oxime, etc. 3. Penzyl ketal systems, such as 2.2-dimethoxy-2-phenylacetophenone, benzyl, hydroxycyclohexylphenyl ketone, etc. 4. Acetophenone derivative systems, such as jetoxyacetophenone, 2- hydroxy-
20 Methyl-1, phenylpropaneacetone, etc. 5, Ketone (ketone-amine type) prefecture side Eva, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxan I-n, 2-methylthioxanthone, '! ! Substituted benzophenone, halogen! Hydrocarbons such as naphthalene, anthracene, phenanthrene, chrysene, etc.6, Nitrobenzene, p-dinitrobenzene, 1,3
．． 5-) dinitrobenzene, p-nitrodiphenyl, m
-Nitroaniline, 2,4-dinitroaniline picramide, 2-chloro-4-nitroaniline, 2,6-sinitro-4-nitroanilinephenol, p-nitrophenol, 2,4-dinitrophenol, 2°4. Amine, nitro, phenolic compounds such as 6-dolinitrophenol8, benzaldehyde, 9-anthraaldehyde, acetophenone, benzophenone, dibenzalacetone,
benzyl, p, p'-diaminobenzophenone, p,
p' -dimethylaminobenzophenone, p, p' -
Ketones 9 such as tetramethyldiaminobenzophenone (Michler's ketone), benzoquinone, 1,2-naphthoquinone, 1,4-
Quinones such as naphthoquinone, anthraquinone, 1゜2-hencyanthraquinone, 10, 7-entrone, 1,9-benzoantrone, 6-phecor-1,9-benzoantrone, 3-phecor-1,9-benzoanthrone, 2-
Anthrones 11 such as keto-3-aza-1,9-benzaanthrone and 3-methyl-1,3-diaza-1,9-benzaanthrone, azo compounds 12 such as 7zobisisobutyronitrile, and mercaptans , organic sulfur compounds such as disulfides 13, various halogen compounds, various oligomers or polymers of various families, various leveling agents such as silicone acrylics, light stabilizers, 11 (plastic agents, surfactants, antistatic agents, various reactions) Catalysts, various pigments,
Fillers, thermal polymerization inhibitors, reducing agents, etc. may be added. Such compounds or compositions curable by actinic radiation, particularly ultraviolet rays, are dissolved in a solvent as necessary, poured into a mold, and cured and molded by irradiation with actinic radiation. In this case, the solvents used include ketone type (e.g. methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic type (e.g. toluene, xylene, etc.), halogen type (e.g. dichloroethane, trichlene, etc.), alcohol type (e.g. methanol, etc.). , ethanol, propatool, methyl cellosolve,
Ethyl cellosolve, etc.), esters (for example, butyl acetate, ethyl acetate, carpitol acetate, butyl carpitol acetate, etc.), hydrogen, etc. are possible. The concentration of the compound or composition thereof that can be cured by actinic radiation is 100% or less, particularly about 20 to 100%. The wavelength of ultraviolet rays used for curing is mainly 200 to 400.
It is said to be about nm. Also, the light intensity is
W/cm - I Kw/cm. Further, the curing time is approximately 1 pLsec to 1 minute, and the curing atmosphere may be in air, inert gas, vacuum, or the like. On the other hand, any mold may be used as long as ultraviolet rays can be irradiated from at least one side. Note that the thickness of the substrate to be cured and molded is particularly important. It is estimated to be about 100 gm to 3+*m. Further, the shape of the base body is usually a disk shape or the like. Note that, if necessary, the solvent is removed by heating before and after curing. In such a case, it is preferable that the substrate has a tracking groove on at least one side thereof so that tracking can be controlled during writing, reading, or erasing. Therefore, it is preferable that the hardening mold has grooves corresponding to the tracking grooves on its surface. In addition, the tracking groove has a depth of 0.01 to 3mm.
, especially 0.05 to 2ILII, and [1] of the groove is 0.
05~50#L11, the distance between the grooves is 0.6~l 00
#Ltm is preferable. A recording layer is laminated on such a substrate. A dye is contained in the recording layer of the optical recording medium of the present invention. There are no particular restrictions on the pigments used; cyanine-based, phthalocyanine-based, naphthalocyanine-based, squalirium-based,
Choline or chorol type, anthraquinone type, azo type,
Any of triphenylmethane-based dyes, pyrylium or thiapyrylium salt-based dyes can be used. However, among these, cyanine dyes have the greatest effect according to the present invention. Among the cyanine dyes, those represented by the following formula (1) are preferred. Formula (I) Φ-L=heavy (X-)m In the above formula CI), Φ and! is an indole ring, a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, a pyridine ring, etc. to which an aromatic ring, such as a benzene ring, naphthalene ring, phenanthrene ring, or quinoxaline ring, may be fused. These Φ and ψ may be the same or different, but
They are usually the same or the same, and one or more substituents may be bonded to these rings. Note that in Φ, the nitrogen atom in the ring has ten charges, and in Φ, the nitrogen atom in the ring is neutral. The skeletal ring of these Φ and city is the following formula [ΦI]
~ [Φ store] is indicated. In addition, in the following, the structure is shown in the form of Φ. 1 1 [Φ■] RI! 1 RI 1 1 1 [Φ] R1 1 In these various rings, the group R+ (R+
, R1') is a substituted or unsubstituted alkyl group or aryl group. Groups R1 and RI bonded to the nitrogen atom in such a ring
There is no particular restriction on the number of carbon atoms of , an alkoxycarbonyl group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a hydroxyl group, a carboxy group, a halogen atom, or the like. Note that when m (described below) is O, S R1 (bonded to the nitrogen atom in Φ) is a substituted alkyl or aryl group and has a negative charge. In general, when Φ and the heavy ring are fused or non-fused indole rings (formula [Φ] to (ΦIV)), the third
At the position, two substituents R2. It is preferable that R3 is bonded. In this case, the two substituents R2 and R3 bonded to the 3-position are preferably an alkyl group or an aryl group, and among these, the number of carbon atoms is 1 or 2. , especially an unsubstituted alkyl group of l. On the other hand, Φ and! At a given position in the ring represented by
Furthermore, other substituents R4 may be bonded. Examples of such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and alkyl groups. Carbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxynon, alkylamide group, arylamide group, alkylcarbamoyl group, arylcarbamoyl group, alkylamide 7 group, arylamide group, carboxylic acid group, alkylsulfonyl group,
Arylsulfonylno^, alkylsulfonamide group,
Arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, cyano group, nitro group, etc. 1
Various q substituents may be used. The number of these substituents (p, q, r, s, t) is usually about 0 or 1 to 4. When p, q, r, S, t is 2 or more, , multiple R
4 may be different from each other. Among these, those having a fused or non-fused indole ring of the formulas [ΦI] to [Φ■] are preferable.
This is because these materials have excellent coating properties and stability, exhibit extremely high reflectance, and have an extremely high readout C/N ratio. On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye;
It is preferably any one of l) to [L■]. Formula (LI) CH= C)l-CH= CH-C= CH-C)I=
C) I-CH formula (Lll) co=cH-co=c-
cH=cH-c'. Formula (Lm) Formula (LV) ■ 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 acetoxy group such as a methoxy group, etc. groups, (, disubstituted amino groups such as dimethylamino group, diphenylamino group, methylphenylamino group, morpholino group, imidazolidine group, ethoxycarbonylpiperazine group, furkylcarbonyloxy group such as acetoxy group, alkylthio group such as methylthio group) R8 and R9 each represent a hydrogen atom or a lower alkyl group such as a methyl group. In addition, among these formulas (LI) to [L■], tricarbocyanine linking groups, especially formulas [Lll), (LIII),
(LIV) and (LV) are preferred. Furthermore, X- is an anion, and preferable examples thereof include I-, Br-', Cl04-, B F4-
+CH3beΣ5o3-, c sentence÷5o3-, etc. can be mentioned. Note that 1m is O or 1, but when m is O, R1 of Φ usually has one charge and becomes an inner salt. Next, specific examples of the cyanine dye of the present invention will be given, but the present invention is not limited to these. Jinsuman exemption = overturn 1L-J engineering U DI , (ΦI) CH3CH3 D2 (OI) CH3CH3 D3 (OI) C2H40HCH3 D4 (ΦI) (CH2)3 SO3-CH3' (
CH2)3 SO3-Na" D5 (ΦII) CH3, CH3 D6 (Φm) (CH2)3 SO3-CH3' (
CH2) 3503- Na ÷ D 7 (ΦIII) CH2CH20HCH3D8
(Om) (CH2)20COCH3CH3D 9 (
Om) (CH2)20COCH3CH3D10 [Φ
m) CH3CH3 DIl (OrI[) CH3CH3 D12 (OI) C,8H3□ C1(3D13 (
Or) C4H9CH3 D14 [Φ■] C3H16ococH5cH3D1
5 (OI) C7)11. CM,,OHCH3,LL
L Y-also -X- -(Lll) H■ -(Lll) HCJlj04 - (,Lm) H1,Br -(Lll) H- -(LII) HClO4 -(Lll) H- one (LII) HClO4 -( Lll) HBr (Lm) -N (Cs Hs)2 1 ClO4'
(L If ) HCfL O4 (Lm) -N(C6H5)2 1 cJ104- (
LII) H■ -(LII) H(, QO4 (Lm) -N (Ca Hs) 2 1 CKLO
4-(LIT), HI Hitoshi Men-j and upper yo'L-' and -11K±D
IG (ΦII) C3HI7 CH3-DI7 (Φ
m) C8H,7CH3-D19 (ΦIII) CH
COOC2H5CH3-714 D20 [Φm] C4H8C1(3-D21 (Φm
] Cl8H3□ CH3-D22 [ΦIII) C
6H8CH3-D23 [ΦI) C17H34COO
CH3CH3-D24 [Φ work] C3H160COC
H3CH3-D25 (ΦI) C8H,7C2H5-
D26 [ΦI] C7H15C2H5-D27 [Φ
II: J C, 7H34COOCH3CH3-D28
(Oll) C8H,6CH,, OCOCH3CH3D
28 [Φn) c 17 H3s CH3-L Y
-Also -ji(- (L II) HC sentence 04 (L II) H- (LII) 'HBF4 (Lm) -N(CaH5)2 1 Cf) -O4(L
II) HC intersection 04 (L II) HC sentence 04 (L II) H1 (Lm) -N (C6H5) 2 1 I (L IT)
HI (L II) HI (L II) HC sentence O4 Totamatsuta Men-y Oriwork 1 upper 1L-11D30 [Φ
II) CHCOOCH3C2Hs 14 031 (Φl1l) C7H,, CH20HCH3D
32 (Φ[11) C7H,4CH,,,0COC,
, Hs CH3D33 [ΦIII) C, □H34C
00C2H5CH3D34 [Φm] C17H35
CH3D35 [Φm] C7H+s C2H5D3
6 [ΦIT] CH3CH3 D37 [ΦrV) CH3CH3 D38 [ΦIV) C4Hg CH3D311 (O
IV) (CH2)2 0COCH3CH3D40 (
'DV) C2H54 D41 [φV) CH3-4 D42 (OVI) C, 2H5 -D43 [φVL) C2HS 5 D44 [φVL) C2H5-5 D45 [φVL) C21 (LLL) ), HC view 04 - (Lll) H0 sentence 04 - (Lll) ' HI (Lm) -N (C6Hs)2 1 I- (LIV)
HI I - (Lll) HI - (Lll) HI - (LTI) HC cross 04 - (Lll) H0 sentence 04 - (LII) Hl -CH3 (Lll) Hl -CH3 (LIT) HI - (Lit) HBr -C1 (Lm) -N(C1lH5)2 1 Br-O
CH3(L II ) HC) I2O3)! , 5O3-
QC) i3 (LIE) HBr Dye j Menyo y and above yo”b-shaku U shaku±D46 [Φ
Vl) C2H5-- D47 [Φ■] C2H3 D48 [Φ■] C2H3 D48 [Φ■] C2H3 D50 [Φ■] C2H3 D51 (ΦVl) C,, H5 D52 [Φ■] C2H3 D53 [Φ■) (CH ) OCOCH3--3 D54 [ΦVl) CH2CH20H-5-CID5
5 [Φ■] C2H3 D56 [Φ[X] C,, Hs --D57 [ΦI
X) C21 (5---D58 (ΦDC) C2H5
-- D59 (OX) C2H5 -- D80 (OXI) cH2C1 (20) (--L Y
Also -X- (L■j l Br (LII) HBr (LI) HBr (Lll) CH3Br (LV) HI Br (LV) HI Br (LVI) l Br (LII[) -N (Ca Hs ) 2' I
CH3C6)1. SO2[LII)HCH3C6H4S
03 (Lll) HBr (LII) HBr (Lm) 0CR31I (L II) HI (Lll) HBr Back entrance J-t・”L D61 [Φ mowing] C,, H5- DBP [Φ creation (CH2) 30COCH3 --D6
3 [to Φ] C2H5- Dθ4 [ΦXll1] CH2CH2CH25O3H
--D65 [to Φ] C2H5- D66 [Φm] C2H5-- 06? (Φ twin) C2H5- D68 [ΦVl] C8H17-4-CH2CH2 (Φ
■) Cl8H3□ -- D70 [ΦVl) C8H17 -- D71 (OV port C8H, □ 5-CID72 (Φ
Vl) C, 8H375-C sentence-0CH D-73 ('1!'VI) Co HI3 (6-OC
HD74 (Φfurther) C3H1□ -5-OCHD75
[ΦV[) C8H, -5-C1L Soil 1 (L II) HI (Lll) -N○COOC2H5°10・1 (L Il
) H1 (Lm) -N(C6H5)2 L Cai04(LI[
1) -N(C8H5)2 1 I(Lll) HBr (Lll) HBr (LII) H1 (LI[I) -N(C8H5)2 1 Br(LSI
) H, 0 sentence 04 (Lm) -N (C8HFI) 2 1 C9,0
4(LII) H1 + (LII) Hr Mi (LrV) -1I (Lm) -N(CsHs)2 1 Brsu wound begging y
h-L RL Kou Red D76 [Φ■] Cl8H37-5-C Interchange D7? [ΦV
I) C8H17- D78 [Φ■) C3H1? - D78 [Φ”) Cl8H3□ -5-cpD80 (Φ
n) C,8H37-5-(,5D81 [ΦVl)
C8Hl? ' -0112 (Φv1) C8H,7-
, -D83 [ΦVl) C8H, Ma - D84 [Φ■) C3H1□ - D85 [Φ■) C11lH3? -D88 (Φ■
) Cl5H27- p87 [Φ■) C13H2□ - D8B [Φ■] C8H17- D89 [Φ■) C3H1? - D80 [Φ■) C111H3□ --L "Two kilns" ShikuLm) -N (C8H5)2 1 Br (L II
) (LII) H, I [LII) HCH3CCH4S03 (Lll) 1 (C sentence C6) 14S03 (LV) HI
I (LVI) HI Br [L■] - (Lm) -N(C8H5)2 1 Br(L II
) HC) 13C6) 14So3 (Lll) HBr (LIT) HBr Mamoru]-NQCOOC2H5"Ben04 (Lm) OCH3' I I (L It ) Hc) I3c6u4so3colorχmanyo"l' l工 Uyu K1091 (Φ ■] C3H
1□ D82 [Φ■] Cl8H37 D93 (Φ scale) C3H1゜D84 [Φ mowing] C3H1□ D82 [Φ mowing) C8H,□ D96 [Φ mowing] C13H2,, -5-CID87
[Φ mowing] C3H17 D98 [Φ mowing] Cl8H37 D88 [Φ store] C3H17 D100 [Φ twin] C3H17 DIOI (Φv) C8I■17 D102 CΦ■] C3H17 D103 (to Φ ] C8H17 0104 (Φr) CHCH0COCHCH3-223 D105 ( ΦI) CH2CH,,OHCH3-DI
Ofi (9m) CH3CH3-L -■-Mata -Eiichi (L II) HC)13C6)14SO3(Lm)
-N (Ca Hs) 2 1 C) I3C6H4
So3 (LTI) HBr (Lll) H, I [LII']-NOCOOC2Hs ”Bent 04 (L I
f ) HI (Lm) −N(CsHb)2 1 Br(Lm) −
N(C8H5)2 1 , Br(Lll) HBr (Lll) HBr (LII) HBr (LII) HBr (Lll) H' -Br (Lll) HC3LOa (Lll) HBr (LVI) Br l C3L() + L people 1-JLL” Lm Engineering 1E-DI
07 (ΦI) C2Hs CH35-C1D108
(ΦI) C2H5CH35-c: D109 (ΦI)
C2Hs CH35-CD+10 (ΦI) C2H
5CH35-CDIll (ΦI) C285CH35
-CD112 (ΦI) C2Hs CH35-CD+
13 (ΦI) C2H5CH35-CDI+4 (Φ
I) C21(5CH35-C0115(ΦI) CH
3CH35-CDII8 (ΦI) CH3CH35-
CD117 (ΦI) n-C4Hg CH35-CD
118 (ΦI) n-C, H2CCH35-CD11
9 (ΦI), (CH2) 4503- CH35-C
(CH2)4 503 H 0120 (ΦI) C2Hs CH35-CLL L
Y- prong -X- 1H5sO2 (LVI) Br l IIH5sO2 (
Lm) C1I CQOaiH5sO2(Lm)' C
fL I Is Hs S02 (Lm) 0 sentences 1
(:)13C6H4So3i H5C02(L VT)
0 sentences I BF43 Hs 502 (LVI) 0
Sentence ICsu04BHbSO2(LVI) C1l・l
8H5302 (LVI) 0 sentences I C) I3C6H,
5O38Hs 502 (L■) 0 sentences 10 sentences 04a
Hs 502 (L ■) C cross 1 1a Hs S
02 (LVI) 0 sentences 10 sentences 04a 85 SO2
(LVI) 0 sentences IC exchange 048H5SO2 (LVT)
C1l-a 85 502 (LVI) N--C-IC-CN
1 - Colored People's World 'PLL Tech 1'7L' b01
22 CΦI) C2HF, CH30123(ΦI)
C2H5c) (3 D124 [ΦI) C2H5CH3 0123 (ΦI] C21 (5CH3 0128' (ΦI) C2) (50H3D127 (Φ
I) C2) (RCH30128(ΦI) C2) (5
CH3 0123 (Φall) CH2=CHC)12 -D131
(Φkneeling) CI (2=CHC) (2-DI32 (Φ
ru) CH2=CHCH2-0133(Φ蹟) CH2
=CHCH2-0134 (Φ seat) CH2=CHCj(
2-D135 (ΦJun) (CH20CI(3-(CH
2) 3N(CH3)2 - Once Sat 1- 1- sentence -X- 5-Ca H2CO (Lm) 0 sentence ll5-C8H5
CO(Lm) Br l H5-Co Hs Co (
Lm) 0 sentences I Cl0t+5-Ca H5CO(L
m) C1I CH3C6)14So35-C6H5C
O(LVI) (, Q I C sentence 045-Ca) (5
Co (L”1lI) 0 sentences 1 r5-Ca H5C
o (LVI) 0 sentences I C)13C6H4So35
-Shizu:6H5Co-ΦI (Lm) HCH3C6)1
,5o3- (LVI) HcH3cθtt,5o35
-0 sentences [Lm) HC) I2O3) 1,5035-C
s H5S02 (LVI) HC)13C6H,5n
35-Ca H5Co (LVI) HCl0a(5-
NO2CL■) 1(C) I3C, H45o36-C sentence, 5-Ca IF, 502 (L[) HCjlOa
'6-N02 Llh Men-y and Knee 1st' u D136 (ΦXI) CaI2 - DI37 (Φ seat) C2H40C, ) (3-DI38
(Φ) CH2=CHCH2-0139 (Φ)
C2H40CH3-D+40 (Φ play) C2H40C
H3-D141 (Φ algae) CH2CHCH2-D14
2 (ΦI) 'CH3('H3D143 (ΦI)
CH3CH3 0144 (ΦI) C2H40COCH3CH3012
3(ΦVl) '(ΦVT-C2H5-[ΦKon] ΦM
lll C2H4C0CH5D148 (Φ■] ΦV
r-C2H5-(OSO'0XIII-(CH2)4SO
3-One and Earth L Y- and -X- 5Ca H5S O2(L V[) 1(Cll3Ce
H4SO35-NO2(LVII[) HCH3C6H
,5o35 NO2, (LVII) HCu045-C
s Hs SO2 (Lm) HC113G8114So
35 C'6 Hs 502 [LVIl) HC,+
104N02 (LVII) HCsu04 CH3Co (LIT) HC104 CH3CO (Lll) HT CH3CO (LTI) HT (5-NO2-ΦVl (Lm)HH 5-C6H5CO-Φ蹟(s-Noz ovr (LVI[) H-5 -Co
H2SO4-OX91 Such a dye can be easily synthesized according to the method described in books such as Dai Organic Chemistry (Breakfast Shoten) Nitrogen-Containing Heterocyclic Compounds I, page 432. That is, first, the corresponding Φ'-CH3 (Φ' represents the ring corresponding to Φ) is heated with excess R and I (R is an alkyl group or an aryl group), and R1 is converted into Φ'. into the nitrogen atom to obtain Φ-CH5I-.
Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst. Further, such a dye is usually contained in the recording layer in the form of a monomer, but may be contained in the form of a polymer if necessary. In this case, the polymer has two or more molecules of one dye, and may be a condensate of these dyes. For example, -0) A single or co-condensate of the above dyes having one or more functional groups such as 1, -COOH, -303H, etc., or a dialcohol, a dicarboxylic acid, or a chloride thereof. diamines, di- or triisocyanates,
There are cocondensation components such as jepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates, and cocondensation products with other dyes. Alternatively, the dye having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dye. In this case, the metal crosslinking agent includes alkoxides such as titanium, zircon, and aluminum; chelates such as titanium, zircon, and aluminum (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and esters thereof, ketoalcohols, aminoalcohols, / - those with active hydrogen compounds, etc. as ligands)
. There are acylates of titanium, zircon, aluminum, etc. Furthermore, -OH group, -0COR group and -COOR
One or more dyes having at least one of JiC (wherein R is a substituted or unsubstituted alkyl group or aryl group) or this and other spacer components or other It is also possible to use one in which the dye is bonded with a -COO- group through a transesterification reaction. In this case, the transesterification reaction is preferably carried out using an alkoxide such as titanium, zircon, or aluminum as a catalyst. Additionally, the above dyes may be bound to a resin. In such a case, a resin having a predetermined group is used, and the necessary The dyes are linked together via a spacer component, etc., depending on the situation. In addition, 44ν Gansho 58-181H7, 58-18
No. 1388, No. 58-183455 and No. 5B-1
The dyes proposed in No. 83456 can equally be used. Furthermore, the recording layer may contain resin. The resin used is preferably a self-oxidizing, depolymerizable or thermoplastic resin. Among these, thermoplastic resins that can be particularly preferably used include the following. i) Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc. ii) Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic 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 llide copolymer, vinyl chloride-maleic anhydride copolymer, acrylic ester or methacrylic ester and vinyl chloride Copolymer, acrylonitrile-1i! Vinyl chloride copolymer, vinyl chloride ether copolymer, ethylene or propylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer graft-polymerized with 1-vinyl chloride, etc. In this case, the copolymerization ratio can be arbitrary. i) Vinylidene chloride copolymer Vinylidene chloride-vinyl 111 copolymer, vinylidene chloride-1-vinyl chloride-7-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc. In this case, the copolymerization ratio can be arbitrary. M) Polystyrene M1) Styrene copolymer For example, styrene-acrylonitrile copolymer (As resin), styrene-acrylonitrile-butadiene copolymer (ABSIt 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. ii) Styrenic polymers such as α-methylstyrene, p-methylstyrene, 2
, 5-dichlorostyrene, α. β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic acid ester. m1ii) Coumarone-indene resin A copolymer of coumaron-indene-styrene. 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. X) Acrylic resins, especially those containing atomic groups represented by the above formula, are feminine. In the above formula, R10 represents a hydrogen atom or an alkyl group, and R20 represents a substituted or unsubstituted alkyl group. , acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer, acrylonitrile-methyl methacrylate copolymer, 7-acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc. In this case, the copolymerization ratio can be arbitrary. ziii) Dai-7 setone acrylamide polymer Dia-7 setone acrylamide polymer made by reacting acrylonitrile with a seven-ton acrylamide polymer. xi) Polyvinyl acetateX) Vinyl acetate copolymers, such as copolymers with acrylic esters, vinyl ethers, ethylene, vinyl chloride, etc. The copolymerization ratio may be arbitrary. ! i) In polyvinyl ether culprit, R10 is a hydrogen atom or has 1 carbon atom
-4 lower alkyl groups, particularly hydrogen atoms or methyl groups are preferred. Further, R2Ll may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R20 is a substituted alkyl group, the alkyl group may be substituted or unsubstituted. The substituent to be substituted is a hydroxyl group,
A halogen atom or an amine group (especially dialkyl amine 7
group) is preferable. 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 copolymers, such as acrylonitrile-vinyl acetate copolymers, such as polyvinyl methyl ether, polyvinylethyl ether, polyvinyl butyl ether, etc. xvii) Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-10, nylon 6-12. In addition to regular homonylons such as nylon 9, nylon ll, nylon 12, and nylon 13, nylon 6/6-676-1
0, nylon 6/6-6/12, nylon 6/6-6/
Polymers such as No. 11 or modified nylon may be used as the case may be. xviii) Polyesters For example, various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipic acid, 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, modified Gliptal resin +11-1, which is obtained by esterifying and modifying Glyptal resin, which is a condensation product of phthalic anhydride and glycerin, with a fatty acid, a natural resin, etc., is also preferably used. X1X) 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. Violet polyurethane resin A 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. 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. xx i i) Cellulose derivatives For example, various esters and ethers of cellulose, such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxye, methylcellulose, and mixtures thereof. Item XX 1) Polycarbonate, for example, polydioxydiphenylmethane carbonate,
Various polycarbonates such as dioxydiphenylproban carbonate. xxi) Ionomers such as methacrylic acid, acrylic acid, etc. Li, Zn, Mgjn, etc. X Sumima) Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetophenone and formaldehyde. X! i) Xylene resin, for example, a condensate of m-xylene or mesitylene with formalin, or a modified product thereof. xxvii) Petroleum resins Cb type, c2, q type, c5-09 copolymer type, dicyclopentadiene type, or copolymers or modified products thereof. X! 111) Blends of two or more of the above l) to xx and ii), or blends with other thermoplastic resins. Note that the molecular weight, etc. of self-oxidizing, thermoplastic, etc. resins may vary. The above-mentioned dyes are usually applied in a weight ratio of 1 to 0, which ranges from 1 to 100. In such a recording layer, there are only two types of quenchers that contain questures.
Reproduction deterioration of N ratio is reduced. In addition, light resistance improves when stored in a bright room. Although various compounds can be used as the que/char, transition metal chelate compounds are particularly preferred because they reduce male deterioration and have good compatibility with dye-binding industry fats. preferable. In this case, the central metals include Ni, Co, Cu, Mn
, Pd. Pt, etc. are preferred, and the following compounds are preferred. 1) Acetylacetonate chelate Ql-INi D Acetylacetonate Ql-2Cu (11) 7SeFlSetoF-ToQ1-3 Mn(II) Acetylacetonate Ql-4Co(1) Acetylacetonate 2) Bisdithio-α-diketo/system represented by the following formula, (Ill to RI4+ are substituted or unsubstituted alkyl groups or Ryl groups) , M is Ni, C
o represents a transition metal atom such as Cu, Pd, Pt, etc. In this case, 1M has a single charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion. In addition, in the following description, ph is a phenyl group, φ4-
11.4-phenyle7 groups, φ' is 1°2-phenyle7 groups, and benz represents that adjacent groups on the ring are bonded to each other to form a condensed benzene ring. 3) Bisphenyldithio-bo8) α represented by the following formula
5) tishikokobusai 1 (51, number transfer - is hydrogen or methyl group,
Alkyl groups such as ethyl groups, halogen atoms such as Ct, or dimethylamino groups. Represents an amino group such as diethylamino group. M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. Furthermore, M in the above structure has a single charge and may form a salt with a cation y (Cat) such as quaternary am/monium ion/etc. Further, K has other ligands bound above and below M. You may do so. Examples of this include the following: :e T: CJ (J :C: :e 工 = 工
Ezu = Engineering Q -: = Engineering === In addition, Japanese Patent Application Laid-Open No. 50-45027 and Patent Application No. 1982-16
Such as those described in No. 3080. 4) Dithiocarbamino acid chelate system represented by the following formula, where +t (91 and 10 represent an alkyl group. M is Ni, Co, Cu, Pd,
Represents a transition metal atom such as Pt. R191, RaQ M 4-s- 04H9N i 5) Compound represented by the following formula, where M represents a transition metal atom. where Cat represents a cation. M Q Cat ---■-Hibiki-■-■■Temporary cheer--Yo-1st, 1. ．．
11.11.1゜Q5-I Ni Q122C1,H,
3N" (CH3). Q5 2 N+ Q122 (C, 119) 4""Q5-
3 Co Q122(C,R9)4N"Q5-4 Cu
Q122 (C, H,), N”Q 5 5 P d Q
122 (0, Hs) 4”Others, patent application 1982 12
As described in No. 5654. 6) A compound represented by the following formula, where M represents a 1M transfer metal atom. death. f! lll and - are CN, C01m, respectively
, C00FL (141, coNall!i , al
lB represents Mataha so, tl. 1 (13 to -η each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group; Q2 represents an atomic group necessary to form a 5- or 6-membered ring; Cat is It represents a cation, and n is 1 or 2. In addition, nine books are listed in Japanese Patent Application No. 58-127074. 7) A compound represented by the following formula, where M represents a transition metal atom, Cat represents a cation, and n is 1 or 2. M Cat Q? -I Ni 2((n-C,R9)3NQ7-2
Ni 2 (n-C□6H, (CH,)3N] In addition,
The one described in Japanese Patent Application No. 127075/1983. 8) Bisphenylthiol system Q8 1 Ni-bis(octylphenyl) sulfide 9) Thiocatechol chelate system represented by the following formula, where M is Ni, Co, Cu, Pd
, represents a transition metal atom such as Pt. Further, 1M has a single charge and may form a salt with a cation (Cat), and the benzene ring may have a substituent. M Cat Q9-I Ni N"(C'4H,). 10) A compound represented by the following formula, (((11 represents a monovalent group, t is θ to 6, M is , represents a transition metal atom, and Cat represents a cation. OM -5 Cat QIO-I Ni HON (n-C, H,). Q 10-2 Ni CH31N (n-C4H,) 4 In addition, patent application As described in No. 58-143531. ttl''I N A1211 Here, in the above general formulas (1) and (1), p, FI2o, FF4 and Misaki each represent a hydrogen atom or a monovalent group. Representation: 44, FIS, R121i and - represent a hydrogen atom or a monovalent group, but F61a and -, FP and -, - and -
may be combined with each other to form a 6-membered ring. Moreover, 1M represents a transition metal atom. 2122 K. 1 Eng. Eng. False 1- = Mo. 1 E. P5 In addition, those described in Japanese Patent Application No. 58-145294. 12) A compound represented by the following formula, where M represents Pt*Nt or Pd,
x, , x, 1. x8. x4 represents 0 or S, respectively. Q12-I Ni O000 Q12-2 Ni S S S S In addition, those described in Japanese Patent Application No. 145295/1982. 13) Compounds represented by the following formula, where W is a substituted or unsubstituted alkyl group or aryl group, RCI, , GLl, - and temporary represent a hydrogen atom or a monovalent group, but - and -, - and Ken), - and B (
4 may be bonded to each other to form a 6-membered ring. Moreover, M represents a transition metal atom. Q13-1 nC, H9HHHHN1 Q13 2 c6■5 HHc2H5HN1Q13-3
nC, H9HHbenz Ni and others, patent application 1982-
As described in No. 151928. 14) Compounds represented by the following formulas: 1) , 1(42) , F$1 and -,
Each represents a hydrogen atom or a monovalent group. R (41) and R (b), R (rumor and -, - and R (44)
may be combined with each other to form a 6-membered ring. Also,

[$1 and [(+41 represent a hydrogen atom or a monovalent group. Furthermore, M represents a transition metal atom. Ql4-1 +1 HHHH-N1 Q14-2 1-I I C,H,OCOH- In addition to Ni, those described in Japanese Patent Application No. 58-151929. 15) Compounds represented by the following formula Coconi, R(511, Hj2) , (((53) , +
54, [$, RH($i and R(- each represent a hydrogen atom or a monovalent group, α5υ, R(5:4, R(5:!l)
, Bt, q i54, R(sd, fs4,
R151tttH oyohiR"i h a('I+i,
may be bonded to each other to form a 6-membered ring. R (5'4 represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. X represents a halogen. ~! represents a transition metal atom. 153392. 16) Salicylaldehyde oxime system a (6) represented by the following formula, where - and Shisu represent an alkyl group, and M is
Ni* Represents a transition metal atom such as Co, Cu, Pd, PL, etc. Ql6-1 i -C3H,1-C5H7NiQ16-
2 (CH・)llCH3(CH,)0. CH, N1Q
16-3 (CH2)0, CR5(OH,)0. CH3
C. Ql 6 4 (CH2)11CH3(CHa)t l
"R3CuQ16-5 C6H, C6H, N1 Q16-6 C, R3C, R5C. Ql6-7 C6H6C, H3-Cu Q16-8. N) (C, H, NHC6H, N1Q16
9 0HOHNi 17) Thiobisfertoki represented by the following formula, where 1
M is the same as above;
Cat) and form a salt (may be formed. Ql 7-1 t-C,HL, Ni N''H3(C,H
,)Ql7-2 t-C,HL, Co N″H,3(
C,H,)Ql7-3t-C,H,,Ni-18) Phosphonous acid chelate system shown by the following formula [
, Sl are the same as above, possible 71) and j((74
represents a substituent such as an alkyl group or a hydroxyl group. Po1), R (marty M Q18-1111ゞ-5-t-C4) (9,6-OH
Ni19) Compounds represented by the following formulas: R (81) , RM , - and R (Sakaki represents a hydrogen atom or a monovalent group) R (8rit -, -1 and -83) , - and - may be bonded to each other to form a 6-membered ring. α噌 and - each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. - is a hydrogen atom , represents a hydroxyl group or a substituted or unsubstituted alkyl group or aryl group. η represents a substituted or unsubstituted alkyl group or aryl group. Z represents any group necessary to form a 5- or 6-membered ring. Represents a nonmetallic atom group. M represents a transition metal atom. an ch O'1 cy(y σ In addition, those described in Japanese Patent Application No. 153393/1983. 20) Compound FL ( g4R(91) where a(91) and It('Ei3 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyl group, an N-alkylcarbamoyl group, an N-arylcarbamoyl group, and an N- Alkylsulfamoyl group, N
- represents an arylsulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and N1 represents a transition metal atom. ,, f'+tla+'n M Q20-1 nC, H8O-1, N1 Q20-2 CH3Cl-1ρ-φ-NHCO tooth In addition, those described in Japanese Patent Application No. 58-155359. In addition to this, other quenchers include the following. 1) Benzoate-based Q21-1 Existing chemical substance 3-3040 (Cinubi 7-1
20 (manufactured by Chipagayi Co., Ltd.)] 2) Hindered amine Q22-1 Existing chemical substance 5-3732 (8ANOL
L8-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]. Each of these clinchers is 0.01 to 1 mole of dye.
It is contained in an amount of about 12 moles, particularly about 0.1 to 1-2 moles. Note that the maximum absorption wavelength of the quencher is preferably greater than or equal to the maximum absorption wavelength of the dye used. 4 In addition, the reproduction deterioration will be extremely small. In this case, it is preferable that the difference between the two is 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 about 0.03 to 10 lumens. In addition, such a recording layer may contain other dyes, other polymers or oligomers, various Of plastics, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and oxidants. An inhibitor, a crosslinking agent, etc. may be contained. 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 1, usually, the compound represented by the general formula (I), 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 substance is generated in the coating solution or after the coating DI 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 qrlj 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, methyl cellosolve, and ethyl cellosolve. Ether systems such as, or aromatic systems such as toluene and xylene. Primers can also be coated on the substrate to improve alkyl halides, such as dichloroethane, tension, thermal conductivity, and the like. As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, etc. can be used. In addition, on the recording layer, various uppermost 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 a reflective layer is not laminated above or below the recording layer. It may have the above-mentioned recording layer, or it may have recording layers on both sides. 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 optical recording medium of the present invention irradiates writing light in pulses from the recording layer side or the substrate side while running or rotating. At this time, pits are formed due to the heat generated by the dye in the recording layer, which causes the self-oxidizing resin to decompose or the thermoplastic resin or dye to melt. The focus point formed in this manner is read out by detecting the reflection of readout light from the recording layer side or the substrate side while the medium is running or rotating. In addition, when the substrate surface has tracking grooves, it is usually necessary to control tracking. While recording or reproducing, reflected light is introduced into a pair of split sensors. At this time, if the beam spot begins to deviate from the recording track section, a phase difference will occur in the reflected light due to the presence of the groove, and the primary light will be biased to one side due to the interference effect, so if the difference between the signals of both sensors is detected, the track error will occur. A signal will be detected. This track error signal is guided to a feedback electronic circuit and is controlled to drive a lens actuator so that the beam spot is always located on the recording track. In such a case, reading and reading may be performed from the base side or from the recording layer side, but it is preferable to perform reading through the body. The pits can be erased by flattening them, and then rewritten. Such erasing and rewriting can be performed repeatedly and stably many times. Note that the pits can be used as writing or reading light. are semiconductor lasers, He-Ne lasers, Ar-lasers, He-
A Cd-laser or the like can be used. Although erasing may be performed using heat or a solvent, it is particularly preferable to perform line erasing or bit erasing using light (laser light). (2) Specific Effects of the Invention According to the present invention, there is little thermal deformation of the substrate due to heat generated by the recording layer during writing or erasing, and the deterioration of the S/N ratio is extremely small. In this case, even when writing or erasing is performed through the substrate, the deterioration of the S/N ratio is extremely small. Also, record H! Since the substrate surface is not damaged by the coating solvent during the first coating, there is very little decrease in reflectance or S/N ratio, and there is also very little deterioration of the S/N ratio over time. Furthermore, since the tracking grooves on the surface of the substrate can be formed during molding, the groove size can be controlled extremely uniformly, and manufacturing is easy. Focus on productivity. Moreover, when the grooves are formed, there is no deformation of the tracking grooves due to coating solvent or heat generation, and trafking control can be performed reliably. Vl Specific Examples of the Invention The present invention will be explained in further detail by showing specific examples of the unpublished '51. Example 1 The following media S1 to S4 were prepared. Sl (comparison) 1.5 mm thick, 30 cIIlφ polymethyl methacrylate sheet surface was stamped with a stamper to a depth of 0.07 p.
+''・Ill O・8 μm grooves formed in a S,<Iral shape. 2 Same shape and dimensions as 51, molded by curing the following composition for 15 seconds with an 80 W/ctm high-pressure mercury lamp. <Composition A>Prepolymer; Monomer made by reacting polyurethane synthesized from polyethylene glycol and 2,4-tolylene diinicyanate with 2-hydroxyethyl methacrylate; 2,4- ) 2-
Initiator: Dialkoxyacetophenone 3 The following composition was urethanized with hydroxyethyl methacrylate and contained triethanolamine in a high-pressure mercury lamp at 100 o/cm.
A grooved product with the same shape and dimensions as 31, molded after curing for 0 seconds. <Composition B) Prepolymer; Epoxy acrylate monomer made from 11,000 molecule epoxy resin, acrylic acid, and methyltetrahydrophthalic anhydride; Pentaerythritol tetraacrylate initiator; 2-tert-butyl Anthraquinone Next, the dyestuff, resin R, and quencher Q shown in Table 1 were dissolved in a predetermined solvent in the proportions shown in Table 1, and the titanium chelate was hydrolyzed onto each substrate. A film was formed and further coated to a thickness of O, O'7p, and ts to obtain various media. In this case, KT is Heron 80 (ketone resin manufactured by Honshu Kagaku Kogyo Co., Ltd.). Further, as the dyes used, the above-mentioned positive and later dyes were used. In addition, the quenchers used are indicated by the positive symbol of those exemplified above. Table 1 also lists the weight ratio of R/D and the weight ratio of Q/D. For each medium produced in this way, this was
While rotating with rpnr, klG aAs-Qa
As semiconductor laser recording light (830n'a+) l#L
It was irradiated in the form of a pulse train at a predetermined frequency and condensing unit output lOmW) to condense the light onto mφ. Each medium was irradiated with a different writing light pulse l], and the pulse l] that gave an extinction ratio of 1.4 was measured, and its reciprocal was taken as the writing sensitivity. The results are shown in Table 1. In this case, the extinction ratio is the degree of attenuation of the reflectance of the medium surface of readout light, which will be described later, at the Virat portion. Separately, writing was performed with a pulse width of 10Onsec. After Kono, l mWc7) semiconductor laser (830nm)
The effects of the present invention are clear from the results shown in Table 1, which show peaks on the disk surface when the readout light is irradiated as a pulse of 1 ILsec width and 3 K) Iz. Example 2 Writing was carried out in the same manner as in Example 1 using ceramic media 2 to 5 of Example 1, and then erasing was performed by heating the medium at 150° C. for 15 seconds using a hot plate. It was confirmed that the data could be successfully erased and rewritten many times with the medium. Applicant TDC Co., Ltd. Agent Patent Attorney Yo Ishii - Continued from page 1 Inventor Takahashi - Husband Tokyo Shikikai

Claims (9)

[Claims] (1) It has a substrate formed by curing and molding a compound or a composition thereof that can be cured by actinic radiation, and has a recording layer made of a dye or a composition thereof on the surface of the substrate. Characteristic optical recording media. (2) The optical recording medium according to claim 1, wherein the active radiation is ultraviolet radiation. (3) Tracking grooves are formed on the recording layer supporting surface of the substrate, claim 1 or 2 q.
The optical recording medium described in +. (4) The optical recording medium according to any one of claims 1 to 3, wherein the groove depth is 0.01 to 3 liters. (5) The optical recording medium according to any one of claims 1 to 4, in which a reflective layer is not laminated on the recording layer. (6) The optical recording medium according to any one of claims 1 to 5, wherein writing and reading are performed through the substrate from the side opposite to the recording layer supporting surface of the substrate. (7) The optical recording medium according to any one of claims 1 to 6, wherein the recording layer has a thickness of 0.01 to 2 JLm. (8) The optical recording medium according to any one of claims 1 to 7, wherein the dye composition contains a resin. (9) The optical recording medium according to any one of claims 1 to 8, wherein the dye composition contains a quencher. (IO) The optical recording medium according to any one of claims 1 to 9, wherein the recording layer is formed by coating.