Optical recording medium

[Detailed Description of the Invention]

■ The background of an invention Technical field The present invention relates to an optical recording medium, especially the optical recording medium in heat mode. Prior art By an optical recording medium being as old as a medium, thru/or reading, since the head is non-contact, a recording medium has the feature of not carrying out wear degradation, and, for this reason, the research and development of various optical recording media are performed. Development of a heat mode optical recording medium is active in respect of the processing procedure by a darkroom being unnecessary and occurring among such optical recording media, etc. An optical recording medium in this heat mode is an optical recording medium which uses record light as heat. It is referred to as one of them. A Fusion-solution, removal, etc. carry out some media with record lights, such as * The and laser, a small hole called a pit is formed, and it is i! There is a bit formation type thing which performs 7 come lumps, records information by this bit, reads this bit, and performs Inspection+13 t and Read with light. In the such pit formation type medium and the thing which makes a light source the semiconductor laser which can miniaturize a device especially before long, what uses as a recording layer material which makes Te a subject has closed most until now. However, that it is necessary that Te system material is harmful and to form high sensitivity more and since it is necessary to make 5J Construction cost cheap more, it changes to Te system and the proposal about the medium using the recording layer of an organic-materials system mainly concerned with pigment and the report are increasing in recent years. For example, as an object for helium -N e laser, it is No. Squalium pigment [Provisional-Publication-No. 5Ei-48221 V. B, Jipson and C, R, JOnes, J, Vac, 5ci - Technol and 18 (1) There are 105 (1981) and a thing using metal phthalocyanine dye (JP,57-820114,A, 57-82095) etc. There is also an example (4! Opening No. 88795 [ 5 [1 to ]) which uses metal phthalocyanine dye as a semiconductor laser river. Each of these makes pigment a recording layer thin film by vapor deposition, and Te system and great difference are not on medium manufacture. However, reflection to the laser of a pigment vapor deposition film - (in the usual method which generally reads l by change (reduction) by the pit of 1 catoptric-light;11 small, and deals in a signal and which is held now, scales cannot do a big S/N ratio.) When the transparent substrate which it had is used as the so-called medium of the air sand inch structure which it unified as the recording layer countered, it pushes in a base and;" come lump and, and read-out are performed, it is 411 about a recording layer, Although it is advantageous at the point that can perform protection of a recording layer, without lowering old lump sensitivity, and storage density also becomes large, such an account M reproduction method is also impossible by a pigment light dress film. this -- the usual base made of transparent resin -- A of refractive-index power t, Ne, and Loving I Sho -- or [ being direct ] -- hunger (it is 1 at a Jelimée Rume Metaglio rate) 5) It is because the reflectance which surface reflectance pushes in the base of Attract (said 4%) and a recording layer to some extent will be about 60% or less, for example by polymethyl methacrylate, so it is undetectable in the recording layer which shows only low reflectance. In order to raise the S/N ratio of read-out of the recording layer which becomes pigment A from a A 1' film, it wears to those, such as A sentence, and is making the reflection film usually intervene between a base and a recording layer. In this case, the 75th place reflection film raises reflectance, and Toward" Yu is [ a reflection film ] for carrying out about a S/N ratio. natural, although a reflection film is exposed by the Pingdu formation, reflectance increases, or one reflection film is removed depending on the case and reflectance is decreased. * -- record reproduction pushed in a base with things cannot be performed. In the recording layer which similarly becomes JP,55-161690,A from IR-132 pigment (Koda, product made by Ri Co.), and polyvinyl acetate, and JP,57-74845,A, the recording layer consisting of l, 1'-Diethyl- 2, 2'-Tori power report Cyanine iodide, and nitroglycerine cellulose -- further alike -- Y, Law, et at, and Appl. Phys, Lett, and 39 (9) The medium which Layering(ed) recording layers consisting of pigment and resin, such as a recording layer set to 718 (1981) from 3.3'-Diethyl- 12-Acetyl thia tetra-Carbocyanine and polyvinyl acetate, by the applying method is indicated. However, the reflection film is needed between the base and the recording layer also in these cases, and it has the same fault as the case of a pigment vapor deposition film at the point which cannot perform record reproduction from the base back side. Thus, in order the record reproduction pushed in a base is possible and to realize a medium with the recording layer of an organic-materials system which has compatibility with a medium with the recording layer which consists of Te system material, the organic materials itself need to show big reflectance. However, there are very few examples which show reflectance high at the monolayer of organic materials without laminating one reflecting layer conventionally. Slightly, the purport that the vapor deposition film of vanadyl phthalocyanine shows high reflectance reports (P, Ki Ma its.). et al, Appl, Phys, and Part A 2B (2) Although it seems that it will be because sublimation temperature is high although 101 (1981) and JP,55-97033,A] are carried out, write-in sensitivity is low. The purport by which high reflectance is shown also with cyanine pigments and merocyanine dye, such as a thia Sole system and quinoline, is although it is carried out and the proposal based on this is made by JP,58-112790,A 27th Japan Society of Applied Physics proceedings 1 p-P-9 (1980) besides report [Yamaki, When it Layering as a coat, the solubility to a solvent is small and it is easy to crystallize, and also to read-out light, especially these pigment is very unstable, and is decolorized immediately, and practical use cannot be presented with it. 57-134170 as which these artificers have proposed previously the purport using the cyanine pigment of an India renin system which also has the high solubility to a solvent, and little [ and ] crystallization, and whose reflectance of a coat it is thermally stable and is high as a single layer film in view of such the actual condition (Japanese-Patent-Application-No. 57-134397-). In the cyanine pigment of an India renin system, it has proposed that introduce a long-chain Alkyl machine into a molecule, and Prevention 11- of a soluble improvement and crystallization is measured (Japanese Patent Application No. No. 182589 [ 57 to ], 57-177778, etc.). It is Prevention 11 about better and the decolorization (reproduction degradation) especially by read-out light in the Mitsuyasu quality. - In order to carry out, it is proposing adding a quencher to the cyanine pigment of an India renin system (57 - 168048 inches of Japanese Patent Application No. etc.). By the way, the cyanine pigment is usually combined with the anion of a cuo4-bamboo hat. The usual transition-metal-chelate compound quencher has combined with cations, such as ammonium ion. For this reason, these unnecessary opposite anions and an opposite cation exist in an account M layer, it is easy to produce acid, alkali, etc. by hydrolysis, and there is a problem in respect of moisture resistance. Since a molecular weight becomes large and Absorbance per middle weight and reflectance become small, only an unnecessary portion becomes disadvantageous in respect of a raise in sensitivity. The object of the TI invention The present invention is made in view of such the actual condition, the main object has very little reproduction degradation, and there is moisture resistance in providing the optical recording medium which has a recording layer containing the cyanine pigment of a good India renin system. Such an object is attained by the present invention of [and an account. Namely, the present invention. It is an optical recording medium which forms in base 1 the recording layer containing the SadamuMitsuyasu-ized cyanine pigment consisting of the joint object of the cyanine pigment cation and quencher anion which are shown by account general formula CI of ↑°, and is characterized by things. = - General type (I) R, R, ' In (account general formula CI of 1-), Z and Z' is substitution or un-n, and D, respectively. An atomic group required in order to complete (7) India renin ring is expressed, R1 and R1' express substitution or an unsubstituted Alkyl machine, an aryl group, or an alkenyl group, respectively, and it is .. L expresses the poly methine connection machine for forming a cyanine pigment, and Q- expresses a quencher anion. ■ Concrete constitution of an invention Hereinafter, the concrete composition of the present invention is explained in detail. The recording layer of the optical recording medium of the present invention contains the SadamuMitsuyasu-ized cyanine pigment consisting of a joint object with India renin-on. In this case, although restriction does not have The in the number of ionic valency of the cyanine pigment cation of an India renin system, and a quencher anion and various combination is ii ability, both are usually univalent. That is, when an India renin system cyanine pigment cation is made into D+ and a quencher anion is made into Q-, a joint object is usually that after D+-Q-. And D+ is denoted by phi"-L-1'. phi -- " -- and a frame of a pile is an India renin ring. Various substitution machines may combine with these rings. And the frame ring of these phi+ and ! is shown by a following formula [phiI] and [!I]. [phi I] ■ 1 [Pile ■] 1 In such various rings, bases R and R' combined with the nitrogen atom in a ring are substitution or an unsubstituted Alkyl machine, an aryl group, or an alkenyl group. There is no restriction in particular in basis R combined with the nitrogen atom in such a ring, and the number of carbon atoms of R1." When this basis is what has a substitution machine further, it is as a substitution machine, A sulfonic group, an alkylcarbonyloxy machine, an alkylamide machine, a Alkyl sulfonamide group, an alkoxycarbonyl group, an alkylamino group, a Alkyl carbamoyl group, a Alkyl sulfamoyl group, Hydroxide 1 (a Carboxy machine, a halogen atom, etc. may be any.) Among these, the Alkylno people especially replaced with the unsubstituted Alkyl machine or the alkylcarbonyloxy machine, the hydroxyl group, etc. are preferred. In the 3rd place of an India renin ring, they are two . It is preferred substitution machines R2 and R3, R2', and that R3" joins together. In this case, as two substitution machine r12.R3 combined with the 3rd place, R2', and R3', it is Alkylno (or it is preferred that it is an aryl group.), And among these, it is preferred the number l of carbon atoms or 2, and that it is an unsubstituted Alkyl machine of l especially. On the other hand, substitution machine R4 of further others and R4' may combine with predetermined - in the ring denoted by phi+ and !. As such a substitution machine, they are a Alkyl machine, an aryl group, a Heterocyclic residue machine, a halogen atom, an alkoxy group, an aryloxy machine, an alkylthio group, an arylthio group, a Alkyl carbonyl group, a Aryl carbonyl group, an alkyloxy carbonyl group, and aryloxy carbonyl nil Oxy. An amide machine, a Alkyl carbamoyl group, the Ali Luca Luba Moyle machine, an alkylamino cram school, An arylamino machine, a carboxylic acid group, Arylsulfonylnon 1 (Aryl sulfo nil)J (they may be various substitution machines, such as a Alkyl sulfonamide group, a Aryl sulfonamide group, a Alkyl sulfamoyl group, an arylsulfamoyl group, a cyano group, and a nitro group.) And when [ whose number of these substitution machines (p, p') is . made about into l~4 ] p.p' is two or more, it may differ in a plurality of R4 and R4' mutually. Cyanine pigment A click * ON has a non-condensing India renin ring, is excellent in solubility, coat nature, and stability, and shows very high reflectance. On the other hand, although L expresses the poly methine connection machine for forming cyanine pigments, such as mono-, Di, Tori, or tetra carbocyanine dye, it is especially preferred that it is either of formula (LI)~(LIX). Formula (LI) ■ Formula (LIX) C Y expresses a hydrogen atom or a univalent basis here. In this case, as a univalent basis, it is Methylo (lower alkoxy groups, such as a low-grade Alkyl machine of a grade, and a methoxy group), A dimethylamine machine, diphenyl Amitno (methylphenylamino machine), Alkylthio groups, such as alkylcarbonyloxy machines, such as Di substitution amino groups, such as a morpholino group, an imidazolidine machine, and an ethoxycarbonyl Piperazine machine, and an acetoxy group, and a methylthio group, Shituno (it is preferred that they are halogen atoms, such as a nitro group, Br, and zero etc. sentence, etc.), R8 and R9 express low-grade Alkyl machines, such as a hydrogen atom or a methyl group, respectively. And a sentence is O or l. In these formula (LI)~(LIX), the trical Bossier Nin connection machine especially formula [LII, (Lm), (LIV), and (LV) are preferred. Below, the India renin system Cyanine color of the present invention, in addition the frame ring of phi1 and psi describe above. Sho" A story'RRR"R D/ I CH3CH3, C2H3 D"2 CH3CH2 O"3 CH3CH2 O"4 CH3CH2 O"5 CH3CH2 O"6 CH3CH2 O"7 CH3CH2 O"8 CH3CH2 O"9 CH3CH2 O"10 CH3CH3 D111 CH3CH2 O"12 C2H5CH2 O"13 CH2cl12ococl, CH2O"CH2CH20HCH214 O" 15 CH3CH2 O"16 CH3CH2 It is H3 to O"17 CH3. D"18 CH3CH2 O"19 CH3CH2 O"20 CH3CH2 O"21 CH3CH2 O"22 C1(3CH3 1' A worker J ground 'LY sentence (LIIH-) 5-C Exchange LIIH - 5, 6 -0-sentence LLTH - 5-OC2H5Lll H- 5-CH3C0Wl L II H-5, 7 - (?-C2[ l LII H-5 and ] H500C: LII H-5, 7-Ch02S LII H-5, 7-CH3LIJ H-) 5,7-CH3C0NI(LLI H-8-CH3C0N)I LII H-5-CH302S Lm N(C6H5)2LHLnH- HLIIH- HL■ H - HLIIIN(C6H5)21 HLII C sees. - 5-CH302S LII H- 5-C2Hs00C: Lll H- 5-CH3LII H- HLUH- Such cyanine pigment cations of an India renin system are I-, and Br, -, CfL04 - It is publicly known as a joint object with Rice anions, such as BF4-, CH3<> SO3-, and zero-sentence 0803-. The joint object of these India renin system cyanine pigment cation and a A dairy anion is easily compoundable according to the method indicated to large organic chemistry (Asakura A shop) nitrogen-containing heterocyclic compound I432 page etc. That is, first corresponding phi'-CH5 (phi' expresses the ring corresponding to above-mentioned phi) is heated with superfluous R and I (R, a Is alkyl machine, or an aryl group), R1 is introduced into the Nitrogen^atom in phi', and phi-CH 5I- is obtained. Or a usual state method of Fisher and a method of Ha ra ld and others (Syn thes i s.) In accordance with the method of 95.8.1981, an India renin derivative is obtained from acetylene alcohol. Subsequently, drying condensation of this may be carried out using unsaturated dialdehyde or unsaturated hydroxyaldehyde, and an alkali catalyst. Or according to a ZINGK reaction, pyridine is made to cleave, guru Takon aldehyde is obtained, it may be made to react to this and 4th class 11! of an India renin derivative, and trical Bossier Nin may be obtained. Although these India renin system cyanine pigment cation takes the form of a monomer, it may usually be a form of Ti:union if needed. In this case, a polymer may have more than dyad [ of an India renin system cyanine pigment cation ], and may be a condensation thing of these India renin system cyanine pigment cation. For example, organic-functions A 1 (they are Germany thru/or a cocondensate, or these about rl of the account India renin system cyanine pigment cation of having [ it ]-one-piece or one or more sorts [ two ] or more" -) of -0H1-COOHl-3O3H grade There is a cocondensate with Co-condensation ingredients, such as dialcohol, dicarboxylic acid or its chloride, Gia Min, Di or triisocyanate, a diepoxy compound, an acid anhydride, dihydrazide, and diimino Carbonate, or other pigment. Or"; it is independent or may crosslink the India renin system cyanine pigment cation which has a functional group of an account by a metal system crosslinking agent with a spacer ingredient and other pigment. In this case, as a metal crosslinking agent, they are Alkoxide, such as titanium, zircon, and aluminum, There are cerates, such as Crisp-1- (for example, thing to which at least Arrangement makes a child beta-Diketone, Ketoester, hydroxycarboxylic acid or its ester, keto alcohol P1 hydrogen compound, etc.), such as titanium, zircon, and aluminum, titanium, zircon, and aluminum, etc. -OH basis, a -0COR basis, and a JCOOR basis (it is R here) One sort or two sorts or more of an India renin system cyanine pigment cation which A i Carry out at least one of being substitution an unsubstituted Alkyl machine thru/or an aryl group, Or what combined other spacer ingredients thru/or other colors and base by the -C0O-basis with the ester exchange reaction is usable. [ this, and ] In this case, as for an ester exchange reaction, it is preferred to make Alkoxide, such as titanium, zircon, and aluminum, into a catalyst. In addition, the above-mentioned India renin system cyanine pigment cation may be combined with resin. In such a case, using the resin which has a predetermined basis, according to the case of the above-mentioned polymer, it is based on a condensation reaction or an ester exchange reaction, or it is based on bridge construction, and an India renin system cyanine pigment cation is connected with the side chain of resin via a spacer ingredient etc. if needed. On the other hand, although the anion object of various quenchers can be used as a quencher anion which constitutes a joint object, since re-, student degradation decreasing especially and compatibility with pigment joint resin are good, it is preferred that it is an anion of a transition-metal-chelate compound. In this case, as a central metal, they are nickel and Co. Cu, Mn, Pd, and Pt'p -- D (better -- To -- the compound of the account of A is preferred especially.) Le system RI thru/or R4 are hydrogen or Methylo (expressing amino groups, such as halogen atoms, such as Alkyl machines, such as an ethyl group, and CfL, or a dimethylamino group, and a diethylamino machine, M expresses transition metal atoms, such as nickel, Co, Cu, Pd, and Pt.) here, The child may combine at least Arrangement of further others with the upper and lower sides of 2M. As this Yo and a Something thing, some are following. l and R2R3R ground L Q-1t HHHHN1 Q-1-2HCH3B, HN1 Q-13H zero-sentence HN[ zero sentence ]1 Q-1-4C1h HHCH3N1 Q-15CH3C83CH3 -- G 13 N1Q-16HC Exchange HHNt Q-1-7C seeing -- zero sentence C -- Exchange C Stand N1Q-1-8HC sentence C Stand C seeing -- N1Q-1-98 (HHC.) Q-1-10HCH30H3HC. Q-1-11HC)13 CH31(N iQ-1-12HH(CH3)2HHN iQ-1-13HN((l)l) N(OH3)2HN i2Q-1-14HN(C)R3)2C)13HN iQ "'1-15 HN(CH3)2 CI HN iQ""1-16 HN(CH)2 HHNi5 2) The screw dithio alpha-diketone system shown with a following formula R5 thru/or R8 express substitution thru/or an unsubstituted Alkyl machine, or an aryl group here, and M expresses transition metal atoms, such as nickel, Co, Cu, Pd, and Pt. In the following statements, ph is Phenyl (it means that, as for phi, l and 4-phenylene group become being on a ring, as for phi', l, 2-phenylene group, and benz become, and the basis which suits combines with each other and forms a condensation benzene ring.), R5R6R7R8M Q-2-N [ 1phi] (CH) ph phiN(CH3) 2 ph N12Q" -2-2pb ph ph ph N1 -- what is shown with Q-2-3phiN(C)132 ph cb N(CH3) 2 ph N s3 following formula -- here, M expresses a transition metal atom and Ql is -C=O-C-CN. Represent. M Q Q-3-I Ni QI2 Q-3-2Ni Ql' Q-3-3Co Q12 Q-3-4Cu Q12 Q-3-5pdQ12 4) What is shown with a following formula M expresses a transition metal atom here and R11 and ill 12 are CN(s), respectively. 13 14 15 18 COR, C0OR, C0NR, R, or 5O2R17 is expressed, and it is 3. H thru/or R17 express a hydrogen atom, substitution, an unsubstituted Alkyl machine, or an aryl group, respectively, and Q2 expresses an atomic group required to form 5 negative or six membered-rings. M A Q-4-I Ni 5 Q-4-2Ni 5 Q-4-4Ni C(CN)2 Q-4-5N i C(CN) 2 5) What is shown with a following formula Q-5-I Ni In addition, the thing indicated to Japanese Patent Application No. No. 127075 [ 58 to ]. 6) The Thiocate call chelate system shown with a following formula M is Nl, Co, Cu, and Pd here. A transition metal atom [ P ] is expressed. The benzene ring may have a substitution machine. 7) What is shown with a following formula R18 expresses a univalent basis here and Stand is theta~6. M expresses a transition metal atom. Q-7-I Ni H0 Q-7-2Ni CH31 8) The Thiobis Fell rate chelate system shown with a following formula Here, M is the same as the above here, and R65 and R68 express a Alkyl machine. R65R6theta M - Q-8-1t-C8H17Ni " Q-8-2 t-C6 HI□Co D2 3 l4 is above 1 in the above-mentioned Kuunchare = ON. (7) 7x Yu 2. beer dithio one 4, system. That of Also l5 is the most preferred. l6 Playback degradation of this decreases further in read-out light, and lightfastness comes -- l7 Oo -- high -- 46 mosquitoes -- ° lower quotation for future used by Ah 6.98, next the present invention -- a law -- the example of JL object of-izing cyanine pigment l9 is given. Dlo l1 12 13 14 15 IEi 17 18 18 Dl free Knee D"22 Q-1-8 D Rei 22 Q-1-12 D"12 Q-1-12 0"22 Q-1-3 D+ 13 Q-1-13 D"15 Q-1-8 I)"2 Q-1-8 D"6 Q-1-8 0"2 Q'-1-12 D"2 Q-1-3 D"2 Q-1-7 0"21 Q-1-8 D"21 Q-1-12 0"19 Q-1-8 D+ 19 Q-1-12 D"20 Q'-1-8 D"j2 Q"'1-I D"22 Q-1-2 D"22 Q-1-13 020D"22 Q-1-14 D21 D"22 Q-1-3 D22 D"19 Q-2-I D23 D"l 4 Q-1-13 D24 D"13 Q-1-16 D25 0+ 15 Q-1-17 D28 D"15 Q-1-18 0270 Chi 17 Q-1-8 D28 D+ 17 Q-1-12 D29 D+ 18 Q-1-12 D30 D"18 Q-1-8 Such a SadamuMitsuyasu-ized cyanine pigment of the present invention is manufactured as follows, for example. First, the cyanine pigment of the cation form combined with the anion is prepared. As an anion in this case (An-), they are I-, Br-, and C104, -, BFa - It may be a CR3<3-303- and C sentence - C> 303-bamboo hat. Such a cyanine pigment is publicly known. It is compounded in accordance with a way method. That is, for example, it may apply to the method of the method indicated to large organic chemistry (breakfast bookstore) nitrogen-containing heterocyclic compound I432 page etc. or Harald et al., and ZINGK correspondingly. On the other hand, the quencher of the anionic form combined with the cation is prepared. Especially as a cation (CaN) in this case, the tetra-alkylammonium of N+4 (CH3) and N"CC4R94 bamboo hat is preferred. These quenchers and - follow Japanese Patent Application No. No. 166832 [ 57 to ], Japanese Patent Application No. No. 163080 [ 58 to ], etc., and are synthetic Be exposed. Subsequently, Mol, such as these cyanine pigments and a quencher, is dissolved in a four to seven polarity solvent. As a polar organic solvent to be used, N and N-Dimethy / L Holm amide is preferred. Leave of the concentration which 0.01 mol / A time grade stops is good. then -- adding a basin system solvent, especially a tree to this -- a crosspiece -- decomposition is made to occur and precipitation is obtained. The size of lO time, with" 2 of the capital of the water to add is superfluous, then it is good. The room temperature~90'C grade of reaction temperature is good. if Mata and a cyanine pigment dissolve in methanol etc. and it mixes them, in [, such as p-Ruensundbon acid chloride or p-chlorobenzene Sulpon acid chloride, / soluble ] being very large -- target stabilization pigment -- Sinking down . Subsequently, if both the liquid phase is separated, filtration dryness is performed and a re-crystal is performed by 4 DMF-ethanol etc., it will be obtained in a SadamuMitsuyasu-ized cyanine pigment. With, dissolve in a methylene chloride etc., the neutral thing which is an intermediate of a quencher cation besides the method of]- is L[ A/]/ m/I[l Made [ cyanine pigment ] into this, and it Contraction r5, and may perform a re-crystal. Or blowing air according to Japanese-Patent-Application-No. 57-16t6H2 No., nickel may be oxidized and salt may be formed as an anionic form. Next, the synthetic example of the SadamuMitsuyasu-ized cyanine pigment of the present invention is given. Synthetic example 1 (composition of DI) 1.3, 3. Bi, 3', 3' - Iogide of product NK[ made from Xamethyl indolino trical Potyanine iodide [Japan photosensitizing dye research new ]-1250/22 (0 or 0005 mol) It is N about 0.25g and the tetrabutylammonium salt (0 or 0005 mol, 0.39g) of bis(3, 4, 8-Tori Chloro- 1, 2-dithio Fell rate)nickel (II) tetra n-butyl Ammonium rum [Mitsui Toatsu Chemicals, Inc. make FA-1006Q-1-8, N After dissolving in 20 m of '-Dimethylform amide sentence and maintaining at 70 degreeC for 3 hours, pour into cold water, filter precipitation, wash in cold water and carry out decompression dryness, 1, 3, 3.1 ', 3 ', 3 ' - Xamethyl indolino trical Bosshanin Bis(3, 4, 6-Drichloro 1, 2-dithio Fell rate)nickel (II) (DI) was obtained. Yield 1ij0.40g (88% of yield) The heating dissolution of this is carried out again at a DMF10m sentence, and 30 m of heat ethanol added 1, and it was neglected, and was made to re-crystallize. 181~182 degrees of mp(s) C (reddish brown) Content nickel was quantified by the atomic absorption method, and the following result was obtained. nickel content (%) calculated value 6 and 15 side constant value 6.07 Pigment stabilizer l:1 Example 2 (composition of D2) of calculated value 4.43 composition as a mixture product NK[ made from Iogide [Japan photosensitizing dye research new ]-125 of D+22 -- and . -SadamuMitsuyasu-ized pigment D2 was obtained, using NIRC-2 by a tetrabutylammonium salt [empire chemicals industrial company of 1-12 like synthetic example 1. Yield+ 91% mp -- gradually -- decomposition (black) nickel content (%) calculated value 7.04 measured value 6.93 Synthetic example 3 (composition of DI5) the Berklo rate of D+19 -- [ -- SadamuMitsuyasu-ized pigment 015 was obtained, using NIRC-2 by a tetrabutylammonium salt [empire chemicals industrial company of product NK[ made from Japanese photosensitizing dye research new ]-2905 Yo UQ-1-12 like synthetic example 1. yield 8o% mp 240"C(decomposition) (black rim color) nickel content (%) calculated value 4.85411 constant Ima ff 4.77 Synthetic example 4 (composition of D4) SadamuMitsuyasu-ized pigment D4 was obtained, using Iogide (product NK[ made from Japanese photosensitizing dye research new ]-125) of D+22, and PA-1005 by tetrabutylammonium salt [Mitsui Toatsu Chemicals, Inc. of Q-1-3 like synthetic example 1. 95% of yield znp 219~220 degreeC(green) nickel content (%) calculated value 6.63 measurement Ima x 6.51 Synthetic example 5 (composition of D7) It used like Xamethyl- 5, 5' - dichloro indri Notori power report Cyanine iodide [Iogide of D/2], and synthetic example 1 to 1 obtained by Police of Harald and ZINGK, 1', 3.3. 3', and 3'-, and obtained SadamuMitsuyasu-ized pigment D7. 75% of yield 205~208 degrees of mP(s) C nickel content (%) calculated value 5.73 measured value 5 and 81 Synthetic example 6 (composition of DlB) 1, 1", 3, 3.3' which were obtained like]- and an account. Xamethyl- 5, 5'-Jetyl hydroxycarbonyl indolino trical Pecianin p-toluene sulfonate (p- of D+20) Ruen sulfonate, and the tetrabutylammonium salt of Q-1-8 are mixed in methanol to 3'-, and they are profit and It was about SadamuMitsuyasu-ized pigment D1B. 70% of yield 192~194 degrees of mp(s) C nickel content (%) calculated value 5.34 measured value 5.49 Synthetic example 7 (014 composition) 1 obtained similarly, 1", 3.3.3', 3' - Xamethyl- 5, 5'-Dimethylsulfonyl indolino trical Bosshanin A Berklo rate and (Berklo rate of D+113) the tetrabutylammonium salt of Q-1-8 are made to be the same as that of synthetic example 1, SadamuMitsuyasu-ized pigment D14 was obtained. 82% of yield 234~236 degrees of mp(s) C nickel content (%) calculated value 5.28Nil constant A ft 5.25 ON ■aX of absorption Speak I and Le in the inside of dichloro ethane of each optical stabilization pigment was almost the same as that of it of a materials cyanine pigment. Such a joint object is a range which does not spoil the effect of the 1 present invention, and may form a recording layer in combination with other pigment. In the recording layer, resin may be contained if needed. If it is considered as the resin to be used, a self-oxidizing quality, solution polymerization nature, or thermoplastics is preferred. The following is among these especially among the thermoplastics which can be used conveniently. i) Polyolefin Polyethylene, polypropylene, poly 4-methyl pen Ten- 1, etc. ii) Polyolefin copolymer For example, an ethylene-vinyl acetate copolymer, an ethylene acrylic ester copolymer, an ethylene acrylic acid copolymer, an ethylene propylene copolymer, an ethylene butene-1 copolymer, an ethylene maleic anhydride copolymer, Echlempropi renter polymer (EFT), etc. In this case, the polymerization ratio of comonomer can be made into arbitrary things. 1ii VCM/PVC copolymer For example, an acetic acid vinyl VCM/PVC copolymer, 1! 1-ized vinyl 11!-ized Vinylidene copolymer, The copolymer of a VCM/PVC maleic anhydride copolymer, acrylic ester or meta-acrylic ester, and VCM/PVC, What carried out the graft polymerization of the VCM/PVC to an acrylonitrile VCM/PVC copolymer, a chlorination vinyl ether copolymer, ethylene or the propylene 11!-ized vinyl copolymer, and the ethylene-vinyl acetate copolymer. In this case, a copolymerization ratio can be made into arbitrary things. i Ma 11!-ized Vinylidene copolymer 31-ized Vinylidene- VCM/PVC copolymer, a vinylidene chloride VCM/PVC =7 Krylo nitrile copolymer, a vinylidene chloride butadiene vinylic halide copolymer, etc. In this case, a copolymerization ratio can be made into arbitrary things. Ma) Polystyrene vi) Styrene copolymer For example, a styrene acrylonitrile copolymer (AS resin), a styrene acrylonitrile butadiene copolymer (ABS resin), A styrene maleic anhydride copolymer (SMA resin), a styrene acrylic ester acrylamide copolymer, a styrene butadiene copolymer (SBR), a styrene vinylidene chloride copolymer, a styrene methylmetaacrylate copolymer, etc. In this case, a copolymerization ratio can be made into arbitrary things. Ma ii styrene type polymer For example, alpha-methylstyrene, P-methylstyrene, 2, 5-dichloro styrene 1, alpha. These copolymers, for example, the copolymer of alpha-methylstyrene and methacrylate ester., such as beta-vinyl Naphthalene, alpha-vinyl pyridine, Acenaphthene, and vinyl anthracene viii) Both ffi union of coumarone-indene resin bear Ron- indene styrene. it) Terpene resin thru/or a pico light, for example, terpene resin which is the polymers of the limonene obtained [ whether it is also alpha-pinene or ], the pico light acquired from beta-pinene. Ri acrylic resin A thing including the atom group to whom it is shown especially with a following formula is preferred. Formula RIO -C)(-C- C-0R2[l ■ In the account type of" Yu, R10 expresses a hydrogen atom or a Alkyl machine, and R20 expresses a Alkyl machine unsubstituted in substitution Light. In this case, as for R10, in the above-mentioned formula, it is preferred that they are a hydrogen atom or a low-grade Alkyl machine with 1~4 carbon atoms especially source of hydrogen 1 child, or a methyl group. moreover -- as for the number of carbon atoms of a Alkyl machine, although R2O may be substitution and which an unsubstituted Alkyl machine, it is preferred that it is 1~8 -- moreover . As for the substitution machine which replaces a Alkyl machine, when R20 is a substitution Alkyl machine, it is preferred that they are a hydroxyl group, a halogen atom, or an amino group (especially dialkylamino group). otherwise, the atom group to whom it is shown by such an above-mentioned formula goes away -- although it may Riyadera, a copolymer may be formed with an atom group and various acrylic resins may be constituted -- usually The independent polymer or copolymer which one sort of the atom group to whom it is shown by the above-mentioned formula, or two sorts or more are A substitute(ed), and is made into a unit will be formed, and an acrylic resin will be constituted. xi) Polyacrylonitrile xii) Acrylonitrile copolymer For example, an acrylonitrile acetic acid vinyl copolymer, an acrylonitrile VCM/PVC copolymer, An acrylonitrile styrene copolymer, an acrylonitrile 1n-ized Vinylidene copolymer, An acrylonitrile vinyl pyridine copolymer, an acrylonitrile methyl methacrylate copolymer, an acrylonitrile butadiene copolymer, a Acrylo trill butyl acrylate copolymer, etc. In this case, a copolymerization ratio can be made into arbitrary things. xiii) Tie acetone acryl amide polymer which made acetone act on Dyer 7-ton acryl amide polymer acrylonitrile. xx Ma polyvinyl acetate xv) Acetic acid vinyl copolymer For example, a copolymer with acrylic ester, vinyl ether, ethylene, VCM/PVC, etc., etc. A copolymerization ratio may be arbitrary. xvi) Polyvinyl ether For example, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc. 1vii polyamide In this case, gay nylon of nylon 6, nylon 6-6, nylon 6-10, nylon 5-i2. nylon 9, Nylon 11, Nylon 12, and nylon 13 grade usual [ as polyamide ], etc. Depending on the polymer of nylon 676-6/6-10, nylon 676-6/12, and nylon 6 / 6-6 / 11 grades, and the case, it may be denaturation nylon. xviii) Polyester fatty series, such as For example, oxalic acid, succinic acid, mullein Toil, adipic acid, and Sebasten acid, 2 31-set acid or isophthalic acid, and terephthal one -- various dibasic acid, such as which harsh aromatic series dibasic acid, A condensation thing with glycols, such as ethylene glycol, tetramethylen glycol, and Hegesa methylene glycol, and a cocondensate are preferred. And among these, especially especially the condensation thing of fatty series dibasic acid and glycols and the cocondensate of glycols and fatty series dibasic acid are preferred. The denaturation glyptal resin etc. which carried out etherification denaturation of the glyptal resin which is a condensation thing of f#, water phthalic acid, and glycerin with fatty acid, a natural resin, etc., for example are used suitably. xix) Each of polyvinyl formal produced by Acetal-izing polyvinyl acetal system resin polyvinyl alcohol and polyvinyl acetal system resin is used suitably. In this case, the degree of acetalization of polyvinyl acetal system resin can be made into duties and the thing of alpha. xx) Polyurethane resin Thermoplastic polyurethane with a urethane bond. The polyurethane resin obtained by condensation with polyurethane resin, division and alkylene glycol which are especially obtained by condensation with glycols and Diisocyanate, and An alkyl range isocyanate is preferred. Summer xi polyether Styrene formalin resin, the ring-opening-polymerization thing of cyclic acetal, polyethylene oxide, glycol, polypropylene oxide, glycol, a propylene oxide ethylene oxide copolymer, poly phenylene oxide, etc. xxii) Cellulose derivative For example, nitroglycerine cellulose, Acetyl cellulose, ethyl cellulose, The various ester of cellulose, such as Acetyl butyl cellulose, hydroxyethyl cellulose, hydroxypropylcellulose, methyl cellulose, and an ethyl hydroxyethyl cell ' sirloin, ether, or these mixtures. zziii polycarbonate For example, various polycarbonate, such as Polydioxy diphenyl methane carbonate and dioxy diphenyl Provins Caponate. xxIv) Eye Onomer Na, such as methacrylic acid and acrylic acid. Li, Zn, Mg salt, etc. xx Ma ketone resin For example, the condensation thing of annular ketone, such as cyclohexanone and the aceto Phenone, and formaldehyde. zxvi xylene resin For example, the condensation thing of m-xylene or mesitylene, and formalin or its denaturation object. xxvii) Petroleum resin C5 system, C9 system, a C5-cg copolymerization system, dicyclopentadiene systems or these copolymers thru/or a denaturation object, etc. xxviii) Above-mentioned i~X! Two or more sorts of Ma's ii blend objects, or blend object with other thermoplastics. The is good. Such resin and the above-mentioned pigment are usually Layering(ed) by the extensive quantity ratio of 1 to 0.1-100 by a Heavy city ratio. In such a recording layer, what was separately indicated to other quenchers 1 No. 181388 [ 58 to ], for example, Japanese Patent Application No. etc., may contain. In order to Layering such a recording layer, generally in accordance with a usual state method, it may paint. And thickness of a recording layer is usually made into 0.03~10 and m grade. in addition -- such a recording layer -- in addition, other pigment, other polymer, or oligomer -- several kinds -- N (a Plastics agent, a surface-active agent, a spray for preventing static electricity, lubricant, fire retardant, stabilizer, a dispersing agent, and an antioxidant -- it may A and ' crosslinking agent etc. may contain.) In order to Layering such a recording layer, on a base, a predetermined solvent is used, and it may apply and may dry. As a solvent used for an application, they are 1, for example, methyl ethyl ketone, and methyl isobutyl ketone, Ketone systems, such as cyclohexanone, butyl acetate, ethyl acetate, the Carpi Tulua Sett, Alkyl halide systems, such as aromatic series systems, such as ether systems, such as ester systems, such as butyl Carpitol acetate, methyl cellosolve, and ethylcellosolve, thru/or toluene, and xylene, and dichloro ethane, an alcohol system, etc. may be used. As the quality of the material of the base which Layering such a recording layer, to a write-in light and read-out light, as long as it is substantially transparent, there may not be any restriction in particular and various resin, glass, etc. may be any. The shape may be any, such as a tape, a drum, and a belt, according to usage. A base usually has a slot for tracking. as quality of a resin material for bases, there is nothing with [, such as polymethyl methacrylate, an acrylic resin, an epoxy resin, polycarbonate resin, Pori Sall John resin, polyether Sarphone, and methyl pen ten polymer, ] A groove -- it permeates and a You-less base is preferred. To these bases, solvent resistance and in order to get wet and to improve a sex, surface tension, the degree of heat conduction, etc., it is preferred to form a foundation layer on a base. As the quality of the material of a foundation layer, they are S+, T i, A sentence, and Zr. I It is preferred that they are an application and the oxide formed by carrying out drying by heating about organic complex compounds and organic polyfunctional compounds, such as n, N f, and T a. In addition, lower i', such as various photosensitive resin!! It can also use as a layer. On a recording layer, various top layer protection layers, one layer of half mirrors, etc. can also be provided if needed. However, as for a recording layer, it is preferred to consider it as a single layer film and not to laminate a reflecting layer on 1 To of a recording layer or the bottom. The medium of the present invention may have the above-mentioned recording layer on the whole surface of such a base, and may have a recording layer to the both sides. They are made to counter with a predetermined gap using two things which painted the recording layer on the whole surface of a base as a recording layer faces each other, it is sealed, and dust and a crack can be prevented from attaching. ■ The concrete operation of an invention Under a run thru/or rotation, the medium of the present invention irradiates with record light in the shape of a pulse. At this time, pigment dissolves and a pit is formed by generation of heat of the pigment in a recording layer. The pit formed in this way is too read under a run thru/or rotation of a medium by detecting the catoptric light of read-out light thru/or penetration light, especially catoptric light. In this case, record and read-out are pushed from the base side in a base, and are performed. And the pit once formed in the recording layer can be eliminated with light thru/or heat, and re-writing can also be performed. As record thru/or a read-out light, a semiconductor laser, helium-Ne laser, Ar laser, helium -Cd laser, etc. can be used. ■ The concrete effect of an invention According to the present invention, reproduction degradation by read-out light becomes very small. And lightfastness also has little characteristic degradation by Toward-1; Si and lightroom preservation. And also when performing elimination and re-writing, there is little degradation of the characteristic and also it carries out Towards also of the preservability. In this case, in the present invention, since the pigment cation and the quencher anion are carrying out the ionic bond, as compared with the time of mixing and using pigment and a quencher, these effects serve as that of - and a People stratified potato more. Even if it does not laminate a reflecting layer, it is A (it can push in the body and can perform writing and read-out satisfactorily.), And solubility is good and crystallization also has it. [ little ] ■ The concrete example of an invention Hereinafter, the concrete example of the present invention is shown and the 1 present invention is explained still in detail. Example 1 Using Coloring shown in the following table 1, this is dissolved into a predetermined solvent and it is titanium chelate compound (T-50 (made by Nippon Soda Co., Ltd.)] is applied). On the acrylics disc substrate with a diameter of 30 cm which hydrolyzed and provided t stratum (0,011Lm), application Layering was carried out at the thickness of 0.061Lm, and various media were obtained. In this case, in Table 1, NC is a nitrogen content of 11.5~12.2%, and nitroglycerine cellulose for viscosity 80 seconds based on JIS K 8703. The content r and H is 10wt%. Aside from this, it is a Berklo rate (D"22) of D/22 because of comparison, And the medium which mixes and contains the tetrabutylammonium salt (Ql-8) of Q-1-8, the Berklo rate (D'22) of D+22, and the tetrabutylammonium salt (Q-1-12) of Q-1-12 was created. The used pigment used Recess illustrated in the account of -1-, and next one. Thus, writing was performed from the substrate back side using the semiconductor laser (830 nm), rotating each produced medium at 900 rpm. In this case, condensing part power usage is 10 mW, and frequency is ? old +z. Subsequently, the semiconductor laser (830 nm and condensing part power usage are IIlnu) was read, it was considered as light, the catoptric light pushed in a substrate was detected, and the C/N ratio was measured by band III 30 KHz with the spectrum analyzer by a Fleet packer F company. It is 1 mW of laser read-out light 1lLsecl]

As a pulse of 3 Klz, change (%) of the reflectance from the base surface side after glaring for 5 minutes by a state of rest, and after saving in RH 40 degrees C 988% for 1500 hours was measured. These results are shown in Table 1. The effect of the present invention is clear from the result of Table 1. Applicant TDK Corp. mark - and Ma representative Patent attorney The sun - Ishikawa -- Bluer 1 . 2;