JPS60204396A - Optical recording medium - Google Patents

Abstract

PURPOSE:To provide an optical recording medium remarkably enhanced in writing sensitivity, wherein a recording layer comprising a cyanine coloring matter having a specified absorption maximum wavelength and a specified reflection maximum wavelength is provided on a base. CONSTITUTION:The recording layer (preferably, not laminated with reflective layers) comprises two or more cyanine coloring matters of formula I or II, wherein phi is a thiazole ring or the like which may be condensed with an aromatic ring, psi is a thiazole ring or the like which may be condensed with an aromatic ring, L is a polymethylene linking group, and X<-> is an acid anion, or a composition of the coloring matters, wherein at least one of the coloring matters has an absorption maximum wavelength of -40-+70nm relative to the wavelength of writing light and a reflection absorption maximum wavelength of -40-+70nm relative to the wavelength of reading light. The substances for forming the recording layer are dissolved in a solvent such as methyl ethyl ketone, and the resultant solution is applied to the base formed of an acrylic resin or the like, preferably, to a ground layer formed on the base and consisting of an organic complex compound or the like, to obtain the desired optical recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Technical Field The present invention relates to optical recording media, particularly heat moat optical recording media.

The first advantage of optical recording media is that since there is no contact between the medium and the writing or reading head, the recording medium will not deteriorate due to wear and tear.
′? Therefore, research and development of various optical recording media are being conducted.

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require development in a dark room.

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, Te-based materials are harmful, and there is a need for higher sensitivity and lower manufacturing costs. Proposals and reports about media using material-based recording layers are increasing.

For example, for He-Ne lasers, squarylium dye [JP-A-58-48221-V] is used.

B. Jipson and C. R. Jones
, J. Vac. Sci.

Technol. , 1B (1) 105 (198
1) ) and metal phthalocyanine dyes (JP-A-57-8
No. 2094, No. 57-82085), etc.

There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Application Laid-open No. 811171115/1983).

In both of these, a recording layer is formed into a thin film by vapor deposition of a dye, and there is no major difference from the Te type.

However, the laser reflectivity of dye-deposited 11Q is generally small, and the current conventional method of obtaining a readout signal by changing (reducing) the reflected light I- due to pits cannot achieve a large S/N ratio. Can not.

In addition, if a transparent substrate with 111 recording layers is integrated with the recording layers facing each other in a so-called air sandwich structure, and writing and reading are performed through the substrate, recording can be performed without reducing the writing sensitivity. Although it is advantageous in that the layer can be protected and the recording density can be increased, such a recording and 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).
, Also, the higher the surface reflectance;
This is because the reflectance through the substrate of the recording layer is about 60% or less in the case of polymethyl methacrylate I, for example, and therefore a recording layer that exhibits only a low reflectance cannot be detected.

Readout S/ of the recording layer consisting of dye groups +1f, i
In order to balance the N ratio, a basic reflective film such as AM is usually interposed between the substrate and the recording layer.

In this case, the vapor-deposited reflective film is intended to increase the reflectance by -E 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 reflectance is reduced by removing the reflective film, but as a matter of course, recording and reproduction cannot be performed through the substrate.

Similarly, in JP-A-55-181680, IR-13
A recording layer consisting of two dyes (manufactured by Kodak) and polyvinyl acetate, and 1.1
A recording layer consisting of '-diethyl-2.2'-tripotocyanine iodide and di-I-rocellulose, and furthermore, Y, Law, et al., Appl, Phy.
s.

Lett, 38 (9) 71B (+981), a recording layer consisting of 3,3'-diethyl-12-7cetylthiatetracarpocyanine and polyvinyl acetate, etc.
Paint a recording layer made of pigment and resin! A medium layered according to the No. 11 method is disclosed.

However, these cases also have the same drawbacks as dye-based films in that they require a reflective film 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 has rIr capability for recording and reproduction through the substrate and has τ exchangeability with a medium having a recording layer made of a Te-based material, The organic material 1 itself needs to exhibit high reflectance.

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

It has been reported that vapor deposition of henadylphthalocyanine 11 shows slightly high reflectance (P. Kivits et al.
Appl, Phys, Part A 2B (2)
101 (1981), Japanese Patent Publication No. 55-97033)
However, the writing sensitivity is low, probably due to the high sublimation temperature.

It has also been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes exhibit high reflectance [Yamaki et al., Proceedings of the 27th Japan Society of Applied Physics tp-p-s
(IHO)), and a proposal based on this was made in JP-A-58-112790, but these pigments have low solubility in solvents and are easily crystallized, especially when applied as a coating film. Furthermore, it is extremely unstable against readout light and immediately bleaches, making it impossible to put it 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. 7-134387, No. 57-134170).

In addition, in other cyanine dyes such as indolenine, thiazole, quinoline, and selenator dyes, long-chain alkyl groups are introduced into the molecule to improve solubility and prevent crystallization. It is suggested that it be measured (
Patent Application No. 57-182588, No. 57-17777E
t, etc.).

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a transition metal compound quencher to cyanine dyes in order to prevent regeneration deterioration (Japanese Patent Application No. 57-188832, No. 57-18804).
No. 8, etc.).

However, even when using these cyanine dyes,
The sensitivity of the layer has increased! be caught.

II. OBJECTS OF THE INVENTION The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording medium with improved recording sensitivity.

Such object is constituted by the invention as described below.

That is, the present invention provides an optical recording medium having a recording layer made of a dye or a composition of dyes on a substrate 1-, wherein the dye is composed of two or more cyanine dyes, and at least one of the dyes is Maximum absorption wavelength is 40 nm to +70 nm of the writing destination wavelength
++m, and the maximum reflection wavelength of at least one dye is from 140 nm to +70 nm of the wavelength of the readout light.

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

The recording layer of the optical recording medium of the present invention contains two or more types of cyanine dyes.

The cyanine dye used in the present invention is not particularly limited, and various types can be used.

However, as cations of various cyanine dyes,
A cyanine dye represented by the following general formula CI) or (II) has a high writing sensitivity and a high reading S/N ratio when contained in the recording layer.

General formula (I) Φ1-L=ψ-Q- General formula [II] Φ=L-! +・Q-The above general formula CI
) and (II), Φ represents a monovalent or divalent residue of a thiazole ring, oxazole ring, selenazole ring, imidazole ring or pyridine ring to which an aromatic ring may be fused, and 1 ψ is, Represents a divalent or monovalent residue of a thiazole ring, oxazole ring, selenazole ring, imidazole ring, pyridine ring or indolenine ring, each of which may have a fused aromatic ring, and L forms a cyanine dye. represents a polymethine linking group for , and Q- represents an acid anion.

Further, m is O or l.

In the isomerized structures represented by general formulas CI) and (TI), Φ is a thiazole ring or an oxazole ring to which an aromatic ring, such as a benzene ring, naphthalene ring, phenanthrene ring, or quinoxaline ring, may be fused. , represents a monovalent or divalent residue of a selenazole ring, an imidazole ring, or a pyridine ring.

In addition, ψ is a thiazole ring, an oxazole ring, a selenazole ring to which an aromatic ring such as a benzene ring, a naphthalene ring, a phenanthrene ring, a quinoxaline ring, etc. may be fused;
Represents a divalent to monovalent 2 residue of an imidazole ring, pyridine ring, or indolenine ring.

These Φ and ψ may be the same ring or different rings.

Note that Φ0 and ψ+ mean that the nitrogen atom in the ring has ten charges, and! and Φ are those in which the nitrogen atom in the ring is neutral.

The skeletal ring of these Φ and city is the following formula [ΦI]
It is preferable that the values are as shown by ~[ΦX] and [ψI] ~ [ψstore].

In addition, in the following, the structure of Φ and ψ is represented by the general formula (I)
It is shown in the form of Φ+- and heavy-.

81 [ΦTV] (R4)Q 10 6 8 ('Pm:l (R4') q l 9 [heavy■) (Ri')q RiO 1 In these various eggs, the nitrogen atom in the ring (゛In the imidazole ring, the group RR' (
R, R') are substituted or 1-I 11 11 is an unsubstituted alkyl group, aryl group or alkenyl group, especially an alkyl group.

Groups R,,R,′ bonded to the nitrogen atom in such a ring
There is no particular restriction on the number of carbon atoms in .

In addition, if this group further has a substituent,
Examples of substituents include sulfone yarn resistance, alkylcarbonyloxy groups, alkylamide groups, alkylsulfonamide groups, alkoxycarbonyl groups, alkylamino groups, alkylcarbamoyl groups, alkylsulfamoyl groups, hydroxyl groups, carboxy groups, halogen atoms, etc. It may be.

Furthermore, when the ring of ψ (ψ+) is a fused or non-fused indolenine ring (formula [ψI] to [ψIV)], two substituents R2' and R3' are attached to the 3-position. It is preferable to do so.

In this case, the two substituents R2' and R3 bonded to the 3-position
' is preferably an alkyl group or an aryl group. Among these, an unsubstituted alkyl group having 1 or 2 carbon atoms, particularly 1, is preferable.

On the other hand, at a given position in the ring represented by Φ and ψ,
Furthermore, other substituents R4 and R4' may be bonded. Such substituents include alkyl groups, arylno, (, heterocyclic residues, halogen atoms, alkoxy groups, alkoxy groups, (, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbonyl groups, Alkylcarbonyloxy group, arylcarbonyloxy group, alkylamido group, arylamide group, alkylcarbamoyl group, arylcaroctamoyl group, alkylamino group, arylamino group, carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonyl group amide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, cyanide group,
Various substituents may be used, such as a nitro group.

And the number of these substituents ( p , q + r +
s, t) are usually O or about 1 to 4. In addition, p. q, r. When s and t are 2 or more, multiple R
4 and R4' may be different from each other.

On the other hand, L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, tri- or tetracarbocyanine dye, and is particularly preferably one of formulas (LI) to [L].

4 Formula (LI) CH=CH-CH=CH-C=CH-CH=CH-CH
↓ Formula (LIX) C t Here, Y represents a hydrogen atom or a monovalent group. In this case, monovalent groups include lower alkyl groups such as methyl (J, Q, methoxy), lower alkoxy (4), dimethylamino, diphenylamino, methylphenylamino, (, morpholino) , imidazolidine 1
(, ethoxycarbonylpiperazine group, etc.), (, alkylcarbonyloxy group such as acetoxy group, alkylthio group such as methylnao group, cyano group,
- It is preferable to use a wide-mouthed material, a halogen source such as Br, or Ci.

Furthermore, R8 and Rq each represent a hydrogen atom or a lower alkyl group such as a methyl group.

And the sentence is 0 or l.

Furthermore, X- is an anion whose preferred CI (3<
') 303-, CM<> 303-, and the like.

Note that m is O or l, but when m is 0, 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.

In addition, in the following, Φ and ψ are the formula % formula % of ψ ^　ni - 0 2 m- 1- 0:, υ　＾ of 11° Engineering Ez:! :　:I:=　-工　　工　工　　线　.

・ O flash Z's c-I engineering 1 1 l I 1 1 M M M M M M M M M , ++:: >> 5 days = = -tJ-111-t, J -〇ω 0 11111+ Ill + 111 + l1l = ○ Engineering 0 6 00: . . Pussy. Ori:e:e O: :e:e Turtle, to the engineering ~ elJ
To he engineering = , ω υ Oω υ ω Oυ ro - to no so -ro at------ Ro lo lo lo lo lo lo ○ υ cnl O- engineering ○ to OC) 0 0 - I -I 1-1 0 tun -CQIIIQ-medium (b) ○ Q oo 0 ゜. Engineering: l: Engineering.

a5 YuQ υ　υ　0：　工　：e’-’：e ”　v　z 22 1 1 し J lu u lu %u -ノ -J 工 O:.

0 0 To O 1u　lu　u　u　u　u　u l:I Mill === Eye= −, J −−−, −J − Engineering − +111111” size 1111111 Engineering η Engineering ○ Engineering ○　o　1　. −. − To E:e Z:e:e:e O: To,. . Two.

○υQυυ○υ /+l/”’IMMM/mM 5 58 5 ：＞　伽　伽　し　伽　伽　佽 RO RO RO RO RO RO RO , e+N:! : u’+. YuQ O: 0: Engineering O zz Wealth 2 1 1 1 1 Eye work = ≧ eye eye; ox １　-　-　-　Pl　-,,! , pu, pu.

0 workman B 1 Tadashi 0:〱〱　　　　　　　・　10:　 Tadashi ==>5: Eyes - -11-t,! −1 -I”-””’-””” Smoke 4 Akebono ■-111-dumb 11c11 υ　Q = Tsubasa = Jin --.

-Do No. La F Group B shi ga shi ga shi ga shi RO RO RO RO RO RO RO 0:eVl ’　e’J　w χ　2 1 ○ l-+1-+kk H Field ME -(1)- 〇 0 00 Engineering NN υ　. .

0 ヱ 工 = 0 工 . . Work Work U C)C) Z ≧ 2 1 11 ni = day! :! Eyes - strokes + - 1 - 1 1 3 C ζ pe 1 1 0 1 1 1 1 Bafu 1111111 ω υ ○ OQ υ ω Kaname Kan Kan Kan early @ Mi+:> 伽 :＞ し 伽 しろ ろRo-ro-ro-ro-ro-ro-ko 〒 = flash--------J U -J -J -ノ -J HO η. 11 υ -riN:I::! :':I: :! : : e-work OQ ω ○
υ 1,,+00:! :○○ ω OQ to 8 to 0 0 0 0 Q η φ r ■ 唖〜 c, lc, IO: N flat flash υ. Engineering.

υ　O0＝　○　工 =:ez　　　O:　.

υ　υ. 0 0 0 11　08　　、11゜ , I = Flash, - 0:0: Flat. ,=, 0 0 00 Q Q op RO RO RO RO RO RO Chestnut Fairy tale 1 , 1, o　ao　+;.

〃〃　　：＞η . 11t, 1.

1　0　It　II Ri　Z　kuku　-ku -V 0 v2 ゜　、　ω　.

Engineering:! :, . , ・υU:! ::! In addition, these cyanine dyes can be easily synthesized according to the Tsuno method described in the number column of Nitrogen-Containing Complex 10 Compounds, page 1432 of Jin 41 Ki-Kagaku (Breakfast Shoten).

That is, first, the corresponding Φ'-CH5 (Φ' represents the ring corresponding to the above Φ) is converted to the excess RT I (RT
is an alkyl group or an aryl group) to form R
1 is introduced into the condensation element -r- in Φ' to obtain Φ-CH5I-. Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst.

These cyanine dyes are usually contained in the recording layer in the form of tli 111, but may be in the form of a polymer if necessary.

In this case, the polymer has a cyanine dye content of 2 or more, and may be a condensate of these cyanine dyes.

For example, a single or co-condensation product of a dye described in 1-, which has one or more 1- of a functional group such as -OH, -COO)I, -3O3H, or a dialcohol. , dicarboxylic acids or their chlorides, diamines, di- or triisocyaners, jepoxy compounds, acid anhydrides, dihydrazides, diiminocarbonates (condensation components and co-condensates with other dyes).

Alternatively, the cyanine 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-based crosslinking agent includes alkoxides such as titanium, zircon, and aluminum, chelate-I, such as titanium, zircon, and aluminum (for example, β-diketones, ketoesters, hydroxycarboxylic acids and esters thereof, ketoalcohols, amino acids, etc.). Examples include alcohols, enolic active hydrogen compounds, etc. as ligands), sialates of titanium, zircon, aluminum, etc.

7 Furthermore, -OH group, -0COR group, and -COOR
One or more cyanine dyes having at least one group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or this and other spacer components or other dyes It is also possible to use a compound in which these are bonded through 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.

In addition, the cyanine dye described above may be bound to a resin.

In such cases, a resin having a specified group is used, and the side chains of the resin are added as necessary by condensation reaction, transesterification reaction, or crosslinking, as in the case of the polymer described above. Cyanine dyes are linked via a spacer component, etc., as appropriate.

The absorption maximum wavelength of at least one of these cyanine dyes used in combination is between w40 and w+
70 nm.

Further, the maximum reflection wavelength of at least one of the other cyanine dyes is in the range of input R-40 to input B+70 nm with respect to the wavelength λR of the read light (same as the normal writing light).

For entry R and entry, usually 830na+ to 7
lf semiconductor laser light of 80n+i, 750r+m
I'm here.

Therefore, for example, dyes with maximum reflection wavelengths of λR-40 to λR+7゜nl11 when input = input w = 830 nm are group A, and dyes with maximum absorption wavelengths of λR -40 to input w + 70 nm are group B. Then you have something like this:

Group A DI, D2. DI2. DI3. DI5゜018.02
0. D25. D26. D29°031, D32. D33
．． D37. D45°D75. D76, D77 etc. Group B D3. D4. D5. D6. D7. D8゜D9,010
, Dll, D14. D16°017, D19. D22.
D23. D24°D27. D28. D30. D31,
D33°D34. D35, D36, D38. D39
.

D40, D41, D42, D4.3, D46
.

D47. D48. D49. D53. D55°D56. D
57. D58. D59, etc. On the other hand, as a dye whose maximum reflection wavelength when hostage input w = 780 nm is input R-40 to input B + 70 nm, the above B
The group is good, and the maximum absorption wavelength is included! -40～in, +7
As a dye of 0 nm, group C of R is preferable.

Group 0 D21, D44. D50. D54. D60°D61.
D62. D63. D64. D65°-D66, D67,
D68. D69,070°D71. D72. D73. D
74. D78゜D79, etc. Regarding the cyanine dyes with 111 rivers, one of the cyanine dyes meets the condition 1-1 only with the maximum reflection wavelength, and the other cyanine dye with the absorption maximum wavelength.
Only the 1M maximum wavelength may meet the above conditions.

Alternatively, both the maximum reflection wavelength and the maximum absorption wavelength may meet the condition -J2.

Furthermore, under the condition that one meets the above conditions only at the reflection maximum wavelength and the other meets the above conditions only at the absorption maximum wavelength, one of the two meets the above conditions for both the maximum wavelength for J-nu and the maximum absorption wavelength. It may be one that meets the conditions.

In either case, the electric shock is improved.

Any number of these dyes may be used in combination.

Also, the ratio is from -40 to +7 at the absorption maximum wavelength.
Total amount of dye of 0 nm and reflected maximum wave input R4 to input H+7
The molar ratio of the total amount of dyes having a diameter of 0 nm may be approximately 8=2 to 228.

0 Such two-positioned cyanine dyes may be combined with other dyes to form the recording layer within a range that does not impair the effects of the present invention.

The recording layer may contain extremely fat, if necessary.

The resin used has self-oxidation property and depolymerization property 1. or thermoplastic resins are preferred.

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

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

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

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

iii) 1g vinyl copolymer, such as vinyl acetate-vinyl chloride copolymer, vinyl-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, acrylic ester or methacrylic ester and vinyl chloride copolymers, acrylonitrile-vinyl chloride copolymers, 111-vinyl ester copolymers, ethylene or propylene-vinyl chloride copolymers,
Such as those obtained by graft polymerizing vinyl chloride to ethylene-vinyl acetate copolymer.

In this case, the copolymerization ratio can be arbitrary.

iv) Vinylidene chloride copolymer - vinylidene chloride-vinyl 111 copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide J (polymer, etc.).

In this case, the copolymerization ratio can be arbitrary.

V) Polystyrene vi) Styrene copolymer For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMAmlM), 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.

Mali) Styrene type 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.

vi) Coumarone-indene resin Coumarone-indene-styrene copolymerization 4 body.

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.

acrylic resin Particularly preferred are those containing an atomic group represented by the following formula.

-0Rn 1 In the above formula, I'l to represents a hydrogen atom -f or an alkyl group, and R20 represents a substituted or unsubstituted alkyl group. In this case, in the above formula, Rl (
l is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group.

Furthermore, R2rl may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R211 is a substituted alkyl group, the alkyl group may be substituted or unsubstituted. The substituent to be substituted is preferably a hydroxyl group, )\rogen atom or an amide group (particularly a dialkylamino group). ' The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one of the atomic groups represented by the above formula An acrylic resin is formed by forming a homopolymer or copolymer in which the species or two or more species are repeating units.

xi) Polyacrylonitrile! ■) Acrylonitrile copolymer such as acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer, acrylonitrile-methacrylate acid methyl copolymer,
Acrylonitrile-butadiene copolymer, Acryloni I
・Relu-acrylic butyl-resistant copolymer, etc.

In this case, the copolymerization ratio can be set arbitrarily.

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

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

The copolymerization ratio may be arbitrary.

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

xvii) Polyamide In this case, polyamides include ordinary homonylons such as nylon 6, nylon 6-6, nylon 6-1O, nylon 6-12, nylon 9, nylon 11, nylon 12, and nylon 13. , nylon 6/6-6/6-10, nylon 6/6-6/12
, a polymer such as nylon 6/6-6/l 1, or modified nylon in some cases. xviii) Polyester, for example, aliphatic acid such as oxalic acid, succinic acid, maleic acid, adipic acid, and cepasthenic acid. Condensates and co-condensates of dibasic acids, or various dibasic acids such as isophthalic acid and terephthalic acid, and glycols such as ethylene glycol, tetramethylene glycol, and hexamethylene glycol. suitable.

Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable.

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

xix) Polyvinyl acetal resin II+ri 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.

0) Polyurethane resin Thermoplastic polyurethane tree with urethane bonds.

In particular, polyurethane resins obtained by the condensation of glycols and diisocyanates, particularly polyurethane resins IM obtained by the condensation of alkylene glycols and alkylene diisocyanates, are suitable.

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

xxii) Cellulose derivatives such as dicellulose, acetyl cellulose, ethyl cellulose, acetyl butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Various esters and ethers of cellulose, such as methylcellulose and ethylhydroxyethylcellulose, or mixtures thereof.

xxiii) polycarbonates such as polydioxydiphenylmethane carbonate,
Various polycarbonates such as dioxydiphenylproban carbonate.

xiii) Ionomer Sodium such as methacrylic acid and acrylic acid.

L　i　,　Z　n　,　M　g　114, etc.

xx Ma) Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetylphenone and formaldehyde.

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

xxvij) Petroleum phase 11FI C5-based, C9-based, C5-cq, co-ITI [spliced fibers, dicyclopentadiene-based, or copolymers or modified products thereof, etc.

Item xxv i) A blend of the above i) to xxvii) or a blend with other thermoplastic resins.

Note that the molecular parts of the tree +1Th may be various.

The weight ratio of such resin and the above-mentioned dye is usually 1.
1 layer at a wide range of gravity ratios from 0.1 to 100.

2. It is preferable that such a recording layer contains a quencher.

As a result, the S/N due to repeated irradiation of readout light is
The reproduction deterioration of the ratio is reduced.

In addition, the light resistance is improved by storing it in a bright room.

Various quenchers can be used, but especially when the dye is excited and singlet oxygen is generated,
- It is preferably a singlet oxygen quencher that undergoes electron transfer or energy transfer from doublet oxygen to become excited, returns to the ground state by itself, and - converts doublet oxygen to a triplet state.

Various singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce acidic deterioration and have good compatibility with dyes. , In this case, the central metals include Ni, Co, Cu, Mn, Pd, P
t and the like are preferred, and the following compounds are particularly preferred.

1) Acetylacetonate chelate system Ql-IN[
(II) Acetylacetonate Ql-2Cu (II) Acetylacetonate Ql-3Mn (m) Acetylacetonate Ql-4Co (II) Acetylacetonate 2)
Bisdithio-α-diketone system 4 represented by the following formula, where RR represents a substituted or unsubstituted alkyl group or aryl group, and M is Ni
, represents a transition metal atom such as Co, Cu, Pd, Pt, etc.

In this case, M 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, φLt
1,4-phenylene group, φ' 1,2-phenylene group, benz represents that adjacent groups in ring I- are bonded to each other to form a combined benzene ring.

) 122222 - Ω dimension III l 1 5 3) Bisphenyldithiol system represented by the following formula, where R to R8 are hydrogen or an alkyl group such as a methyl group or an ethyl group, a halogen atom such as C1, or dimethyl An amine group such as an amino group or a diethylamino group, and M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt.

In addition, M in the above structure has a single charge and may form a salt with a cation (Ca t ) such as a quaternary ammonium ion. may be combined.

Examples of this include the following:

cIJOIJ ~ ~ toC1σ σ σ σ 1 + + 'JC') groan ω to ω ■ :111
1 111111 C') C') e') I"l's evil ψ ψ ΩC
il:y σ σ σ σ σ σ σ σ In addition, those described in Japanese Patent Application Laid-Open No. 50-45027 and Japanese Patent Application No. 163080-1982.

4) Dithiocarbamic acid chelate system S /°・1.・°＼ (R1]) 2 N-CM C-N(R10) 2\/
\/S Here, R9 and R10 represent an alkyl group.

Further, M represents a transition metal such as Ni, Co, Cu, Pd, or Pt.

5) What is shown by the following formula Here, M represents a transition metal atom, and Ql is 0 and Cat represents a cation.

Sex-Ship-Cat Q5-I N i Ql2 2C161133N” (
C) 3) 3Q 5-2 N i Q 12 2C (C
,I(8)4N+Q 5-3 COQ 12 2C(C
4H8) 4N+Q 5-4 Cu Q 12 2C(C
4)+8)4N+Q5-5 Pd Ql2 2C(CH
)N”84 In addition, those described in Japanese Patent Application No. 58-125654.

6) Those represented by the following formula, where M represents a transition gold atom, R and R12 are CN, COR"?1 c o o n , c ON R": R16 or 5O, respectively.
2R17 represents 4, H to n17 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 represents a cation, and n is 1 or 2.

Z, Z Ofu B c, l hard work 8,,≧ -IN　e’)　Moan　[F]　■ II　I　I+　1 T Co U Co μ Co 6 Co ■ 6 F l:y　σ　cy　σ　σ　U In addition, those described in Japanese Patent Application No. 58-127074.

7) Compound represented by the following formula Here 1M represents a transition metal atom, Cat represents a cation; n is 1 or 2.

M Cat Q 7- I N i 2 ((n-C4Hs)3N)
Q 7-2 N i 2 (n-C, 6H33(C:H
3) 3N) In addition, those described in Japanese Patent Application No. 58-127075.

8) Bisphenylthiol-based C8-IN+-bis(octylphenyl) sulfide 9) Thiocatechol system represented by the following formula, where M is a transition metal such as Ni, Co, Cu, Pd, or Pt. represents an atom.

Further, M has a single charge and may form a salt with a cation (Cat), and the benzene ring may have a substituent.

-Cat Q9-I Ni N" (C4Hg) 410) Compound represented by the following formula, where R18 represents a monovalent group, the letter is 0 to 6, M is a transfer metal atom and Cat represents a cation.

8 MR sentence Cat Q 10-I N i HON (n-C, H8).

Q 10-2 N i CH31N(n-C4H8)4
What is described in Japanese Patent Application No. 143531/1983.

ll) Compounds represented by the following formulas: In the above formula, R, R, Rh and R23 are each 20 21 2
2 represents a hydrogen atom or a monovalent group, R24, R25, R26 and R27 are water k Bit
r represents a monovalent group, but R and R, R and R, R26 and n27 24 25 25 2B may be bonded to the tail to form a hexagonal ring.

Further, M represents a metal transfer material.

6ri ΣI ;; 1 ko 1 ko ko 1 ko koi 1 ko ko σ σ In addition, what is described in the patent application No. 1973 s-t 45294 s+.

12) Compounds represented by the following formula, where M represents Pt, Ni or Pd, Xl,
X2, X3, X44f, 0 or S
represents.

M Entering balls

+3) Compound represented by the following formula, where R31 is a substituted or unsubstituted alkyl group or aryl group, R, R, R and R35 represent a hydrogen atom 32 33 34 or a monovalent group, R32 and R33, 3334
3435 R,! :R, R and R may be bonded to each other to form a 66 ring.

Moreover, M represents a transition metal atom.

31 32 33 34 35 RRRRM Q l 31 nCaHs H)I H)I NIQ1
3-2 C6H3H25 HCHHNi Q13-3 nC4H3II Hbenz Ni and others described in Japanese Patent Application No. 151928/1983.

14) Compounds represented by both formulas below 41 41 43 R, R, R and n44 are each Represents a hydrogen atom or a monovalent group, 41 42 42 43 43 44 R and R, R and R, R and R are It may also bind to t4 to form a 6-day ring.

5 Furthermore, R and R413 represent a hydrogen atom or a monovalent group.

Furthermore, M represents a migrating metal atom.

R41R42R43 One-R44! l! 45! ! 48 M Q14-1)I HHHH-Ni Q, 14-2 HHCHOCOHH-Ni7 In addition, those described in Japanese Patent Application No. 58-151929.

+5) Compounds shown in the description W? 51 Ba 51 52 53 54 55 Here, R, R, R, R, R.

56 57 R, R, and R58 each represent one hydrogen atom or a monovalent no, (, but 5+ 52 52 53 53 54 R and R, R and R, R and R, R and R, R, !-R and R5? and R58 are 55 58
58 5? r1- may be bonded to form a 6-membered ring.

X represents halogen.

M represents a transition metal element -f.

2 In addition, those described in Japanese Patent Application No. 58-1533921).

16) Salicylaldehyde oxime system shown in f description, 61 Here, R and R61 represent an alkyl group 0, and M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as Pt.

Q 16-1 1-C3H71-C3H7N iQ l
6-2 (CH) C) I (CH2),,CH3N
i113 Q 16-3 (CI) CH(co2),,CH2
O.

113 Q16-4 (OH) Cl-1(C)I, )1□C
HaC.

113 Q16-5 C6H5C6H6N1 Q16-8 CB H5C8H5C0 Q16-7 C6H5C6H5Cu Ql 6-8 NHO2H5NHO2H6N 1Q16
-11 0H-OHNi 17) Thiobisferrate chelate system represented by F description l■ Here, M is the same as above, and R65 and R66 represent an alkyl group. Further, M has one charge and may form a salt with a cation (Cat).

566 R, RM Cat Q 17 1 t-CHN I N” H3 (C4H9
)8 1? Q l 7-2 t-CHCON”H3(C4H8)8
1? Q17-3 t-CHNi-81? 5 +8)-1110 phosphonic acid chelate system reduced by F description, where M is the same as above and u? 1 and R7
2 represents a substituent such as an alkyl group or an aqueous group.

172 AND-1ER-Picture 111111111 ¥Q 18-
1 3-t-C)l, 5-t-C,II9.6-O
HNi9 6 18) 1 Compound 878 represented by each formula? Here, R, R, R and n84 are water 81 82 8
3 Represents an elementary atom or a monovalent group, but 81 82 82 83 83 84 R and R, R and R, and R and R may be bonded to form a hexacyclic ring.

R85 and R88 each represent a hydrogen atom, a substituted or unsubstituted alkylnoA, or an aryl group.

H86 represents a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group or aryl group.

R87 represents a substituted or unsubstituted alkyl group or aryl group.

Z represents a group of nonmetallic atoms that can safely form a 5- or 6-membered ring.

M represents a transition metal atom.

9 ■　ω Engineering 0 In addition, those described in Japanese Patent Application No. 58-153393.

20) Compound represented by F description, where n91 and R82 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyl group, an N-furkylcaroctamoyl group, an N-arylcaroctamoyl group, It represents an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and M represents a transition metal atom.

Q20-1 nC4Hg CH3N 1Q20-2 C
H3CH30-φ-NHCONi and others, patent application 1984-
As described in No. 155359.

In addition to this, there are other quenchers such as those listed in F.

21) Benzoate type Q 21-1 Existing chemical substance 3-3040 (Tinuvin-120 (manufactured by Ciba Geigy)) 22) Hindered amine type Q22-1 Existing chemical substance 5-3732 (SANOLI)
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Each of these quenchers contains 0.01 to 1 mole of dye.
It is contained in an amount of about 12 moles, particularly about 0.05 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.

This results in extremely low regeneration and deterioration.

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

In order to miniaturize the device, it is preferable to use 750.780.830 as a light source for writing and reading.
nm semiconductor laser or 633 nm He-NE
Since it is preferable to use a laser or the like, the maximum absorption wavelength of the main term oxygen quencher is 680 nm or more, especially 680 nm or more.
80-1500, even more preferably 800-150
Preferably, it is 0 nm.

Furthermore, when the absorption coefficients of the dye used (the effective value when used) and the -principal oxygen quencher at the wavelength of the readout light are εD and εQ, respectively, εD/εQ must be 3 or more. is preferred.

In addition, when using two or more kinds of dyes in combination, the maximum absorption wavelength of the dye and the six points are an arithmetic mean effective value depending on the concentration.

With such a value, the excitation of the quencher during irradiation with the readout light becomes extremely small, and the deterioration of regeneration due to main term oxygen becomes extremely small.

Furthermore, the quencher may form an ionic bond with the dye.

A quencher having such absorption characteristics is appropriately selected and used depending on the light source and dye used.

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 2 pm. Alternatively, when forming a recording layer using only a dye and a quencher, vapor deposition, sputtering, etc. may be used.

The thickness of the recording layer is 0.04 to 0.127 Lm, particularly 0.04 to 0.127 Lm.
It is preferable that it is 05-0.087zm.

Below 0.041 Lm, especially Q and 03 ILm, both absorption and reflection are small, and neither writing sensitivity nor reproduction sensitivity can be made large.

If it is 0.12 μm or more, the pre-group will be buried, making it difficult to obtain a tracking signal. In addition, bit formation is not easy (and writing sensitivity is reduced).

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

To form such a recording layer, it may be applied onto the substrate using a predetermined solvent and dried.

Incidentally, examples of solvents used for coating include methyl ethyl ketone and methyl isobutyl ketone.

Ketones such as cyclohexanone, esters such as butyl acetate, ethyl acetate, carpitol acetate, and butylcarpitol acetate, ethers such as methyl cellosolve and ethyl cellosolve, aromatic systems such as toluene and xylene, and halogenated systems such as dichloroethane. Alkyl type,
Alcohol-based materials may be used.

The material of the substrate on which such a recording layer is provided is not particularly limited as long as it is substantially transparent to writing light and reading light, and may be any of various resins, glass, etc.

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

Note that the substrate usually has tracking grooves.

In addition, as the resin material for the substrate, a substrate without grooves such as polymethylmethacrylate-I, acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyethersulfone, methylpentene polymer, etc. is suitable. be.

In order to improve the solvent resistance 1, wettability, surface tension, thermal conductivity, etc. of these substrates, it is preferable to form a base layer on the substrate-F. The material of the base layer is Si, T.
It is preferable to use an oxide formed by applying an organic complex compound or an organic polyfunctional compound such as i, Al, Zr, In, Ni, Ta, etc. and drying it by heating.

In addition, various photosensitive resins can also be used as the base layer.

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 the reflective layer is not laminated above or below the recording layer.

The medium of the present invention may have the recording layer (1) on one surface of such a substrate, or may have recording layers on both surfaces thereof.

In addition, two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, which is then sealed tightly to prevent dust and scratches. You can also do it like this.

7. Basic Function of the Invention The medium of the present invention is irradiated with recording light in a pulsed manner while traveling or rotating. At this time, due to the heat generated by the dye in the recording layer, the dye melts and pits are formed.

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

In this case, recording and reading are performed through the substrate from the substrate side.

Then, the pits formed in the --El recording layer can be erased with light or heat to perform rewriting.

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

8 ■Specific effects of the invention According to the present invention, writing sensitivity is significantly improved.

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

Examples The pigmentation and quencher Q shown in Table 1 below are shown in Table 1.
Dissolve this in a predetermined solvent and apply a titanium chelate compound (T-50 (manufactured by Nippon Soda Co., Ltd.)).
Diameter 30cm with base layer (0,01=) after hydrolysis
Various media were obtained by coating a layer of 0.06#Lm on an acrylic disk substrate of 0.06#Lm.

In this case, the absorption maximum wavelength and reflection maximum wavelength of each dye are as follows.

Also, (λW=input R)-40=7901m.

(In,=In R)+70=8901111.

D31 815 860 D33 820 860 D52 700 870 D36 880 970 D32 780 870 D37 780 870 In this case, in Table 1, NC is nitrogen content 11.5-
12.2%, viscosity 80 based on JIS K 8703
Second nitrocellulose, its content is 10wt%
0.2 weight was added to 14 total dyes.

While each of the media thus produced was rotated at 900 rpm, writing was performed from the back side of the substrate using a semiconductor laser (830 nm), and the sensitivity was set at 411 with a power of 10 mW at the converging section.

The sensitivity is determined by the minimum pulse l](ns
) is the reciprocal of

1 On the other hand, writing was performed at a condensing power of 10 mW and a frequency of 2 MHz.

Next, a semiconductor laser (830 nm, condensing power of 1
mW) as readout light, the reflected light through the substrate was detected, and the C/N ratio was measured using a spectrum analyzer manufactured by Hu17 Tutop Card Co., Ltd. at a band width of 30 KHz.

Further, the reflectance from the back side of the substrate was measured using a laser readout beam of 1 mW.

These results are shown in Table 1.

2 JP-A-Sho GO-204396 (30) From the results in Table 1, the effects of the present invention are clear.

Applicant TDC Co., Ltd. Agent Patent Attorney Yo Ishii -・ 4 Continuation of page 1 ■Inventor: Takahashi - Husband, Tokyo Chuo Type 1 Company @Inventor Akihiko Kuroiwa Inside Tokyo Chuo Shiki Company

Claims (1)

[Scope of Claims] (1) An optical recording medium having a recording layer made of a dye or a composition of dyes on a substrate -1-, wherein the dye consists of two or more cyanine dyes, at least one of which is a cyanine dye. The absorption maximum wavelength of one dye is one-fourth of the wavelength of the writing destination.
nmN+70nm, and the reflection maximum wavelength of at least one dye is one wavelength of the readout light from 40n to +70nm.
An optical recording medium characterized by being n-sized. (2) The cyanine dye has the following general formula (I) or (TI
) The optical recording medium according to claim 1, having the structure shown in (a). General formula (I) Φ0-L=9 (X-) m General formula (I
I) Φ-L='P'' (X-)m (the above general formula (I
) and (II), Φ represents a monovalent or divalent residue of a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, or a pyridine ring to which an aromatic ring may be fused, and ψ respectively A thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, which may be fused with an aromatic ring,
Represents a divalent or monovalent residue of a pyridine ring or indolenine ring. (L represents a polymethine linking group for forming a cyanine dye, X- represents an acid anion, and m is 0 or l) (3) the recording layer consists of a dye composition, Claim 1 or 2 including a quencher
(4) The optical recording medium according to claim 3, wherein the quencher is a chelate compound of a transition metal. (5) The optical recording medium according to any one of claims 1 to 4, wherein the recording layer is made of a dye composition, and the dye composition contains a resin. (6) The optical recording medium according to any one of claims 1 to 5, in which writing and reading are performed from the back side of the substrate. (7) The optical recording medium according to any one of claims 1 to 6, in which a reflective layer is not laminated on the recording layer.