JPS60168691A - Optical recording medium - Google Patents

Abstract

PURPOSE:To reduce deterioration due to erasing or reproduction, by a method wherein a recording layer comprising a liquid crystal, an indolenine cyanine dye and a quencher is provided between a base provided with an electrode layer and a transparent base provided with a transparent electrode layer. CONSTITUTION:The recording layer comprising a liquid crystal, an indolenine cyanine dye and a quencher is provided between the base provided with the electrode layer and the transparent base provided with the transparent electrode layer, thereby obtaining an optical recording medium. The indolenine cyanine dye is a compound of the formula, wherein each of phi and psi is an indolenine ring, a thiazole ring, an oxazole ring, a selenazole ring or the like to which an aromatic ring may be bonded, L is a methine chain, X<-> is an anion, and m is 0 or 1. The quencher is a chelate compound of a transition metal.

Description

[Detailed description of the invention] ■ Background of the invention Technical field The present invention particularly relates to an optical recording medium having a liquid crystal layer.

Prior Art and its Problems In recent years, the development of erasable and rewritable optical recording media has been active, and one of them is known as one that utilizes the phase transition of liquid crystal (SPIC420 p194 to p199, etc.).

Such a medium is constructed by providing a liquid crystal layer, such as smectic, between a first substrate having an electrode layer and a transparent electrode having a transparent electrode layer.

By irradiating such a medium with a laser beam, the electrode layer of the first substrate generates heat and is rapidly cooled, causing a smectin-Kunematic phase transition, etc. in the irradiated area, and recording. A dot is formed and written. Furthermore, when the medium after reading is irradiated with a laser beam for reading, the reading can be delayed due to light scattering at the recording point.

Rough 1. By applying an electric field or heating or removing heat between the electrodes of the medium after the infiltration, the medium undergoes a transition to the original smectic phase, etc., and is erased9).
Ichiban Kikaei (becomes Noh)

In addition, laser irradiation can be performed while applying heavy pressure, or erasing can be performed by heating without applying voltage.

When such a liquid crystal layer contains a dye such as cyanine dye, recording sensitivity and readout S/N ratio improve. However, cyanine dye has poor light resistance, and sensitivity and S/N ratio increase due to self-generation and erasure. There is an inconvenience that it deteriorates.

II. OBJECTS OF THE INVENTION An object of the present invention is to improve the recording sensitivity and read S/N ratio, and to reduce deterioration due to erasure and f-reduction in a heat mode rewritable optical recording medium having a liquid crystal layer. There is a particular thing.

Such objective 1] is achieved by the following invention.

That is, the first invention is an optical recording medium characterized by including a recording layer having a liquid crystal display between a substrate having an electrode layer and a transparent substrate having a transparent electrode layer.

A second invention is an optical recording medium characterized by having a substrate having an electrode layer, and a layer containing light having a recording layer containing liquid crystal between the transparent substrate having an electrode layer and a recording layer containing a liquid crystal.

A third invention includes a photoanine dye and a quencher having a recording layer containing a liquid crystal between a substrate having an electrode layer and a transparent substrate having a transparent electrode layer, the electrode layer and/or the transparent substrate having a recording layer containing liquid crystal. The optical recording medium is characterized in that an alignment agent layer is provided on an electrode layer.

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

The medium of the invention has first and second substrates.

The first substrate is made of glass, various resins such as polycarbonate, various photosensitive resins, various metals, etc., and an electrode layer is formed on its surface.

The layer 81 may be any layer made of a conductive material, but is usually a metal oxide such as indium tin oxide (ITO), indium oxide, or tin oxide; All, Au, Cr, Pb, etc. Single metal; Cr alloy.

TbFeCo, TbDyFe, GdTbFe.

GdFe, GdCo, TbFe, GdFe.

Rare earths such as TbFe0 (Gd, Tb, DV.

HO, etc.) and transition metals (Fe, Co, etc.) alloy thin films.

Alloys such as MnB i , MnCuB I; 5bSe, T
Chalcogenides such as eAsGe and TeOx; Group II-IV compound semiconductors containing Mg and Ca (
MgSi, MgGe, MgSn.

Ca Si, Ca Sn, Ca Pb), Zn, Cd
Group II-V compound semiconductors (ZnAs, Zn
As, Zn5b.

CdAs, CdSb, Mgsb), ri-Vl group compound semiconductors containing Te, V-Vl group compound semiconductors (CdTe
, SbTe); Cerment (glass resistive film containing metals such as Cr and Au), etc., with a thickness of about 0.01 to 2 m.

Note that if a light absorption layer is provided on such an electrode layer, the recording sensitivity and reproduction S/N ratio will be further improved to obtain preferable results.

In this case, the light-absorbing layer may be of various types, such as a layer made of various dyes, but is particularly preferably made of a cyanine dye system and a quencher, which will be described later. At this time, the deterioration due to ilT raw and 7Ill is further reduced.

Such a light absorption layer has a thickness of 0. It has a thickness of about 5 to 5 μm and is formed by vapor deposition, sputtering, and coating/I3A'7.

The light-absorbing layer may contain other dyes, functional polymers or Olycomer-1, surfactants, antistatic agents, stabilizers, crosslinking agents, binders, initiators, sensitizers, An alignment agent, an alignment treatment agent, etc. may be contained.

On the other hand, the second substrate is a transparent substrate, such as glass, polycarbonate, acrylic, or epoxy.

It is formed from various transparent resins such as various photocuring resins.

Then, on this second substrate, indium oxide, IT
O (indium tin oxide), tin oxide, An, Au, C
A transparent or semitransparent electrode layer made of various metals such as r, Cr alloy, Pb, etc. is formed to a thickness of about 0.001''-1H μm.

The first and second substrates are integrated via a spacer or the like so that the electrode layers supported by both substrates face each other, and form a cell, in which a liquid crystal is stored. .

The liquid crystal to be used may be nematic, cholesteric, smectic, etc., but there are no particular restrictions, but in terms of sensitivity and S/N ratio, it is a smectic liquid crystal, and has a smectic-eintropic transition, a smectic-nematic transition, or a smectic-nematic-einthrobby transition. It is preferable that the material undergoes a black transition.

As such liquid crystal compounds, the following are suitable.

(1) Azomethine compound C3 (n=θ~3) 8 CH3 C2H5 C3H7 C4H9 C3Hn CgH1g cis -(CH2)7CH=CH(fm2)7CH3
CI3-(GHz)1tCH=C)l(GHz)7”
3Cl0 K) Engineering (Ca Ha 0H) 2) Azo compound L CIf Ca H90N=NOOCa H13LC
12C2H60N-N (Σ0COCa Hu (3) Azoxy compound LC+8 r corner (4) Ester compound (5) Biphenyl compound L C20C3Hll %ΣCN LC21C7HtaO &Σ0N LC22C1l HI7<Σ(ΣCN LC23C9H19K) (ΣCN L C24Cl0H21ζΣ(ΣCN L C25Cu H23MCN LC28Cl2H25<=8CΣCN LC27Ca H170xΣCN L C28C9H190X8xCNLC29Cl0
H210(Σ(ΣCN L C30C11HzI OMCN L C31C+2 H2S O&ΣCNLC39Ca
H170 Befu H mouth > COOCa H7LC42C5H anal
Σc3H7 (6) Bicyclohexyl type L C44R-(X(XR2)il R2 C2R5--CN C4Hg --0N CbHu--CN C4R9--Coobe=ΣC3H7 (7) Tetrazine type C4Hq O-C5Hll - C4R90-Ca Hls - Cb HlI O-CbH15- C5HlI O-C7Hls - C8R130-C7Hls- (8) Buenylcyclohexane-based L046 R5&ΣR6 R5R6 C5HIJ -9C2H2 O2HjJ -%C3R7 (n=2-6) (n=2-6) Like this Liquid crystals are usually poured into cells either alone or in combination, with the addition of other nematic or cholesteric liquid crystals, and optionally electrolytes.
For example, methyl ethyl ketone, 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,
The liquid crystal layer is dissolved in a solvent such as alcohol and stored in a cell, and the thickness of the liquid crystal layer is 0. The thickness is about 01 to 100 μm.

Furthermore, the liquid crystal layer contains one or more cyanine dyes and a quencher.

As the cyanine dye, it is preferable to use an indolenine dye represented by the following formula (I).

Formula (I) Φ-L=ψ (X-) 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! may be the same or different, and various substituents may be bonded to these rings.

However, Φ and! One and both of these are indolenine rings to which aromatic rings may be fused.

In addition, in Φ, the nitrogen atom in the ring has ten charges, and in V, the nitrogen atom in the ring is neutral.The skeletal rings of these Φ and city have the following formulas [ΦI] to [ Φ■], at least one of which is shown below as [Φ
〕～〔Φ■〕.

In addition, in the following, the structure is shown in the form of Φ.

In these various rings, a group R1 (R+
, R+ ′) if, a conversion t? , c is an unsubstituted alkyl group or aryl 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 this group. In addition, when this group further has a substituent, examples of the substituent include a sulfonic acid group, an alkylcarbonyloxy group, an alkylamitono, (, and an alkylsulfonamide). It may be any of a group, an alkoxycarbonyl group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a hydrophilic group, a carboxy group, a halogen atom, etc.

In addition, when m described below is 0, the group R bonded to the nitrogen atom in Φ is a substituted alkyl or aryl group,
and - has an electric charge.

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 group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylcarbamoyl group, arylcarhexamoyl group, alkylamino group, arylamino group , carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group,
Various substituents may be used, such as a cyano group and a nitro group.

The number of these substituents (P+Q+r+s, t) is usually about 0 or 1 to 4.
When r q * r + s + t is 2 or more,
The plurality of R4s may be different from each other.

Note that cyanine dyes in the present invention are [Φ] to [Φ
(2) Since it has at least one fused or non-fused indole ring, it has excellent stability, and also has extremely high recording sensitivity and reading C/N ratio.

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

Formula (LI) CH=CH-CH=CH-C-CH-C) I=CH-C
H↓ Formula (L W ) CH=CH-C=CH-CH↓ Formula [L■) CH-(j,=CH Here, Y represents a hydrogen atom or a monovalent group. In this case, a monovalent group The groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, disubstituted amines such as dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxycarbonylpiperazine groups. It is preferable to use a fulkylcarbonyloxy group such as acetoxy group, a fulkylthio group such as a methylthio group, a cyano group, a nitro group, or a halogen atom such as Br or C.

Furthermore, R8 and R9 each represent a hydrogen atom or a lower alkyl group such as a methyl group.

And the value is 0 or l.

In addition, among these formulas (LI) to (LVI), tricarbocyanine linking groups, especially formulas [Lll), (LI[[]
, (LIV), (LV) are preferable.

Furthermore, X- is an anion, and preferable examples thereof include I-, Br-, CL04-, and B F4-.

CH3<> 303-, C sentence 0503-, etc. can be mentioned.

Note that 1m is O or engineering, 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.

Color Emperor Reduction vB Engineering 1 Top' Ahead L'b DI (ΦI) CH3Cu2 O3 (ΦI) CH3Cu3 O3 (ΦI ) C2H40HCu3 O4 (4) I) ((, (iHz '!, s g 8z
2 Na" Cu3O5 (ΦII) CI (3Cu3 O8 (4'III) ((: old (=Komeng: N8°.13
D7 (Φm) CH2CH20HCu3O8 (ΦII
I) (CH2)2 0COCH3Cu3O9 (Φm)
(CH2) 20GOCI (3CH3014(Φm)
CH3CH3 014 (()m) CH3CH3 014 (Φ engineering] Cl8H37CH3 014 [ΦI) C4H9CH3 014 (ΦI) CHOCOCH5CH316 D15 (ΦI) C7H1, CH20HCH3, and soil L Y- or -X - - (LIE) HI - (Lll) HC or 04 - (Lm) Hj Br - (LIE) H- - (Lll) HC or 04 - (Ln) H- - (Lll) HC104 - (Lll) HBr (Lm) -N (Cs Hs) 2 1 CfLO
a-(Lll) HC or 04 - (Lm) -N (C615)2 1 CJ104
- (Lll) HI - (Lll) HCl0a (LH) -N CCe H5)2 1 CjLOa-
(Lll) HI dyeμ
1[[) C8H,7CH3-D18 [9m) CH
COOC2H5CH3-714 D'20 (9m) C,H9CH3-D21 (ΦI
[I) C, 8H3□ CH3-D22 [ΦIII)
C4H8CH3-D23 [ΦI] CHCOOCH
3CH3-734 D24 [ΦI] CHOCOCH3CH3-16 D25 [ΦI] C8H17C2H5-D26 [Φ
■] C7H15C2H5-D27 [ΦH) CHC
OOCH3CHs -734 D28 [ΦII] CHCHOCOCH3CH381
62 D29 [Φ”] C17H35CH3-L Y-Meng
-X- (L II) HC intersection 04 (L II) H- [L■] -N N-COOC2Ht, 1 - (Lll)
HBF4 (LII[) -N (Co Is) 2 1 Cl
0a(L II ) M CI Oa (Lll) HCfLO4 (Lll) ' H1 (Lm) -N (C6H5)2 1 I(L II
) HI (L II) HI (L II) HC intersection 04 [L”]-N N-COOC2 [61I [L■) -N
N-COOC2H51C sentence 04 pigment positive Φ, 'i'
R1, R1" R2, R3 RID30 [ΦII)
CHCOOCH3C2Hb -714 D31 (9m) C7H,4CH20HCH3-D3
2 [9m] C7H,4C1 (20COC2H5CH
3-D33 [9m) CHC00C,,H5CH3-
734 D34 (9m) C, 7H35CH3-D35 [Φ
■] C7H15C2H5-D3B (ΦIV) CH
3CH3- D37 [ΦIV) CH3CH3- D38 [ΦIV) C4H9CH3-D38 [ΦI
V) (CH2)2 0COCH3CH3-D40 [
ΦI) CHCHOCOCHa CH3-2 D41 [ΦI) CH2CH20HCH3-D42
[9m) C) 13 CH3-L Y I
HI I [L■) HI (L II) Le I (Lll) HCl0a (L II) HC Mi04 (L II) HI (Lit) H0 sentence 04 (Lll) HBr (L■) Br l C1Oa Color Industrial Emperor Men Yo'iFR upper -11L' Danri, -11D4
3 [ΦI) C2H5CH3 D44 [Φl] C2H5CH3 D45 [ΦI] C2H5CH3 D46 [ΦI) ' C2H5CH3D47 (ΦI
) C2Hs CH3 D48 [ΦI) C2H5CH3 D49 [ΦI] C2H5CH3 D50 [ΦI] C2H5CH3 D51 [ΦI) CH3CH3 D52 [ΦI] CH3CH3 D53 [ΦI] n-C4Hg CH3D54 [Φ
I) n-C6H,3CH3D55 (eI) ()HdayaS8s-, CH3D58 [ΦI] C2H5CH3 D57 [ΦI) CH3CH3 1L Y I X 5-C6HhSO2 (LVI) Br l H5-C6
Hb 302 (LIn) C1I Cl045-C1
lH5SO2(Lm) C1I H5-C6) 1530
2 (Lm) C110H3CB) 149035-C6
H6302 (LVI) 0 sentences I BF45-Co H
6302 (Lm) C1I Cl0a5-Co H55
02 (LVI) Cl I H5-Ce H6302 (
Lm) CI I C) 13C:8H,5O35-C6
H6302 (LVI) 0 sentences I Cl045-Cs
Hb 302 (LVI) Cl 1 engineering 5-C6H+;
302 (LVI) 0 sentences ICl045-C6H5
502 (Lm) Cl I C1045-, eHhS
O2 (L■) CJl 1-5-C6) 15302
(Lm) N--C-C-ON 1 -5-C6Hh
302 (L■) N-Yumi-yumi-CM 1-Colored Emperor Rejection Menko-obai Un-Eng 1 upper' k-Yu 1 58 (eI) C2
H6CH3 D59 ((II) C2H6CHa D80 (OI) C2H6CH3 D81 (ΦI) C2H5CH3 D82 (OI) C2H6CH3 De3 (()I) C2H5CH3 D64 [ΦI) C2H5CH3 Dflfl! (ΦI) CH3CH3D87 (OI
) CH3C)13 D88 (OI) C2H40COC)13 CH3-
and 4 L-1--l-X- 5-Co Hs Co (Lm) 0 sentences 1 engineering 5-Co
H5CO(Lm) B r L H5-Ca H5G
o (Lm) Cl I Cl045-Cs Hs C
o (Lm) C1110H3(:8)14So35-
Co Hs CO(L■) CIL I Cl0a5-
C6H5CO (LVI) C1I H5-C3H5CO
(LVI) C1I CH3CeH45O35-Co
[5GO-I I (Lvl) H, CH3C6H45
O3CI43Co (Lll) HCn0aCH3CO
(Lll) Hl CH3Co (Lll) Hx Such a dye can be easily synthesized according to the method described in Nitrogen-Containing Heterocyclic Compounds, page 1432, Narita, Dai-Ifa Kagaku (Breakfast Bookstore).

That is, first, the corresponding Φ'-CH3 (Φ represents the ring corresponding to the above Φ) is heated with excess R+ T (R+ is an alkyl group or an aryl group) to form R1.
is introduced into the nitrogen atom 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.

Furthermore, such a dye is usually contained in the recording layer in the form of a conjugate, but may be contained in the form of a conjugate, if necessary.

In this case, one polymer has two or more molecules of one dye, and may be a condensate of these dyes.

For example, it may have one or more functional groups such as -OH, -COOH, -503H, etc., and may be a condensate of these dyes.

For example, single or co-condensates of the above dyes having one or more functional groups such as -OH, -COOH, -803H, etc., or dialcohols, dicarboxylic acids or chlorides thereof, diamine, di- or triisocyanate,
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 agents include alkoxides of titanium, zircon, aluminum, etc., chelates of titanium, zircon, aluminum, etc. (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and their esters, ketoalcohols, aminoalcohols, enols) those with active hydrogen compounds, etc. as ligands)
, titanium, zircon, aluminum, and other acylates.

Furthermore, -OH group, -0COR group OYOHY COOR
One or more types of 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 A combination of -Coo- and -Coo- by transesterification can also be used.

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 cases, using a resin that has a specific group,
As in the case of the above polymer, the side chain of the s1 fat is subjected to a condensation reaction, transesterification reaction, or crosslinking.
The dyes are linked via a spacer component, etc., if necessary.

In addition to such dyes, quenchers are included.

This reduces reproduction deterioration and erasure deterioration of the S/N ratio due to repeated irradiation with read light and erase light.

In addition, light resistance is improved by storage in a bright room.

Various quenchers can be used, and transition metal chelate compounds are particularly preferred because they reduce regeneration and erasure deterioration and have good compatibility with dyes. In this case. , as the central metal, N1. Co, Cu, Mn, Pd, PL, etc. are preferred, and the following compounds are particularly preferred.

l) Acetylacetonate chelate Ql-I N1
(II) Acetylacetonate Ql-2Cu(II) Acetylacetonate Ql-3Mn(II) Acetylacetonate Ql-4Co(II) Acetylacetonate 2
) where R is a bisdithio-α-diketo,
1 to R4 represent a substituted or unsubstituted alkyl group or aryl L (M is Ni, Go, Cu, P
d, Pt, etc.) S represents a transition metal atom.

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

In the following description, ph is a phenyl group, φ is a 1,4-phenylene group, φ' is a 1,2-phenylene group, and ti and benz are groups adjacent to each other in ring J2 or L
This represents that L is bonded to form a condensed benzene ring.

21; Iris; = σ σ ClCl σ 3) Bisphenyldithiol system expressed in the t-formula 8 Here, H to R is hydrogen or t±methylnon,
Alkyl group with ethyl group, halogen source with Cl group (-
, or represents an amide group such as a dimethylamino group or a diethylamine group, and M is Ni, Co, Cu, Pd, P
Represents a transition metal atom such as L.

In addition, M in the structure shown in "2" may form a salt with a cation (Cat) such as a quaternary ammonium ion with a ton of 4:I. A ligand may be attached.

Examples of this include the following:

σ σ σ σ σ σ σ σ CI σ121;;
;; 2;2 ;;; σ σ 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) Dithiocarbamine ugly chelate system represented by the following formula Here, R9 and )l10 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 and Cat represents a cation.

L Moxibustion-Cat Q5-I N i Q122CHN” (C)13)3
633 Q 5-2 N i Q 122C(C4H8)4N”
Q 5-3 Co Q '7 2C (C4H9), N"
Q 5-4 Cu Q 122C (C:4H8)4N”
Q 5-5 P d Q 122C(C,,H5)4N
6) Those represented by the following formula: where M represents a transition gold atom, and R11 and R12 are CN and COI't, respectively.

5 16 represents C0OR, C0NR, R or 5O2R17, R13 to R17 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a aryl group, and Q2 is a group necessary to form a 5- or 6-membered ring. Cat represents a cation, and n is 1 or 2.

χ Portrait χ t , , engineering . 8 1 22220ta -C5JeQ size -■ It　　　　II　1 0 Co Co ■ ω ω Of　σ　aI　σ　σ　σ In addition, those described in Japanese Patent Application No. 58-127074.

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

Cat Q 7- I N i 2 ((n-C4H8)3N)
Q 7-2 N i 2 (n-C16) 133 (C)
I3) 3N) In addition, those described in Japanese Patent Application No. 58-127075.

8) Bisphenylthiol system Q8-IN+-bis(octylphenyl) sulfide 9) Thiocatechol chelate system represented by the following formula, where M is Ni, Co, Cu, Pd, Pt'9.
represents the transition metal element -f.

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

M Cat Q9-I Ni N” (C4H9) 410) Compounds reduced by the following formula: where R18 represents a monovalent group, the letter is 0 to 6, and M is a transition metal atom and Cat represents a cation.

M R181Cat Q to-t N iHON(n-C4H8)aQ 1
0-2 N i CH31N (n-C4Hs) 4° Described in Japanese Patent Application No. 143531/1983.

11) Compounds represented by the following formulas -1 and 2 in the general formulas (I) and (II)
0 2+ 22 and R, R, R and R23 are each hydrogen atom -
r or a monovalent group, and 24 25 28 R, R, R and R27 each represent a hydrogen atom or a monovalent group.

24 25 25 28 28 27 R and R, R and R, R and R Fi,! J- may be bonded to form a 6-negative ring.

Moreover, M represents a transition metal atom.

Σ1 ;; Country 1 Engineering Engineering 1 Engineering Engineering Qlll Engineering Engineering 1 Engineering Engineering σ α In addition, the following are mentioned in Japanese Patent Application No. 145284-1984 +2
) Compounds represented by the formula C, where 1M represents PL, Ni or Pd, and X+
, K2, K3, and K4 represent 0 or S distortion.

Gender-xL KL K1 X1 Q12-I Ni OOO0 Q12-2 Ni S S S S In addition, those described in Japanese Patent Application No. 58-145295.

13) Compound 1 represented by the following formula, where R is a substituted or unsubstituted alkyl group or aryl group, and R32, R33, R34 and R35 represent a hydrogen atom or a monovalent group, but R32 and R33, R33 and R3
4, R34 and R35 may be combined with each other to form a 6-membered ring.

Moreover, M represents a transition metal atom.

11 12 13 Death-15N Q13-1ncHHHHHNi 9 Q13-2CHH)I C)l HNi65 25 Q13-3 ncHHHbenz Xi9 In addition, those described in patent application No. 1t/J 58-151928-14) Compounds R, R,
R and R44 each represent a hydrogen atom or a monovalent group, but 41 42 42 43 43 44 R and R, R and R, and R and R are bonded to form a 6-membered ring may be formed.

Furthermore, R and R48 are hydrogen atoms or 5 Represents a monovalent group.

Furthermore, 1M represents a transition metal atom.

! l! 41! ! 42R43R44! l! 45! ! 46M
Q14-IHHHHH-Ni Q l 4-2 HHc4H7oco HHN + Others described in Japanese Patent Application No. 151929/1982.

15) Compound represented by the following formula , 51 5! 52 53 54 55 Here, R, R, R, R, R.

56 57 R, R, and R58 are each a hydrogen atom or 1
51 52 52 53 53 54 R and R, R and R, R and R, 55565El 57 R and R, R and R, and R57 and n58 combine with each other to form a 6-membered ring. Good too.

R59 represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.

X represents halogen.

M represents a transition metal atom.

21; Two 2I = -I Eni J1 D.

u',,l　eh　 144 11 d d U1. .

Mi 1 Go 2 Engineering 5 to le In addition, those described in Japanese Patent Application No. 58-153392.

18) Salicylaldehyde oxime system represented by the following formula, 61 where R and R61 represent an alkyl group 0, and M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as pt.

Ql6-1 1-C3H71-C3H7N1Q16-2
(CH) C)l (aH2)1□CH3N t11
3 Ql6-3 (CH) (H(CH) CH,C.

2113 2113 Q l 6-4 (CH) CH(OH2)1□CH3
C.

113 Ql6-5 C8H5C6Hs N1 QlB-6C6H5C6H5C.

Ql 6-7 CB H5C6H5CuQl 6-8
NHC6H5NHC (3H5N 1Q16-9 0H
OHNf 17) Thiobisferrate chelate system represented by the following formula, where M is the same as above, and R65 and R2O represent an alkyl group. Further, M has a single charge and may form a salt with a cation (C:at).

65 66 Dan-ichiyo”D M Cat Q 17-1 t-C8H,7N i N”H3(C4
H8) Q 17-2 t-C8H, □Co N”H3(
C4H9) Ql 7-3 t-C3H,7N + -1
8) Phosphonous acid chelate system represented by the following formula, where M is the same as above, and R71 and R72 represent a substituent such as an alkyl group or a hydroxyl group.

172 Shaku-ichie RM Q I 8-1 3-t-CH,5-t-CaHa
, 6-OHN i8 '8) Compound Rh represented by the following formulas where R, R, R and R84 are hydrogen 81 82
83 represents an atom or a monovalent group, and R81 and R82, R82 and R83, n83 and R84 may be bonded to each other to form a 6-membered ring.

R85 and R88 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.

R86 represents a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group or aryl group.

t+87 represents a substituted or unsubstituted alkyl group or aryl group.

Z is the non-gold 1 necessary to form a 5- or 6-membered ring.
Represents 4 atomic groups.

M represents a transition metal atom.

zl　;　z　z N1 1 1 1 tl e: tl e: ul　：　：　： σ　σ　σ In addition, those described in Japanese Patent Application No. 58-153393.

20) Compound 1 represented by the following formula: where R and R82 are each a hydrogen fragment f':
a, substituted or unsubstituted alkyl group, aryl group, (, acyl group, N-alkyl group, (, N-arylcarbamoyl group, N-furkylsulfamoyl group,
It represents an N-arylsulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and M represents a transition metal atom.

R81R" 2M Q20-1 nC4Hg CH3N iQ 20-2
CH3CH30-(b-NHCON iIn addition, those described in Japanese Patent Application No. 155359/1982.

In addition, other quenchers include the following.

l) Benzony I/Series Q21-1 Existing chemical substance 3-3040 (tinuvin-
120 (manufactured by CH/Hekaigy Co., Ltd.)] 2) Hindered amine Q 22-1 Existing chemical substance 5-3732 (SANO
LLS-770 (manufactured by Hankyo Seiyaku Co., Ltd.)] Each of these quenchers has a concentration of 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.

The maximum absorption wavelength of the quencher is preferably equal to the maximum absorption wavelength of the dye used.

As a result, (1) aging and deterioration are extremely small.

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

In addition, dichroic dyes can also be added.

The following dichroic dyes are particularly suitable.

l, merocyanine dye I 2 3 4 DI3 2. Anthraquinone dye I4 15 19 20 21 22 23 24 25 2fl 33 D36 38 39 40 41 42 43 45 46 D4? D48 D49D54 5oD55 51D56 52 58 4, styryl dye 59 60 DB+ 5, azomethine dye CL, etc., tetrazine type, methine type, squarylium type, etc.The mixing ratio of liquid crystal and cyanine color clay is 1 in molar ratio.
; About 0.01 to 0.8.

Furthermore, the liquid crystal layer contains various alignment agents and various polymers or oligomers such as polycarbonate.

Various plasticizers, various stabilizers, etc. may be contained.

In addition, the electrode layer of the first substrate-1- and/or the second
When an alignment agent layer is provided on the electrode layer 1 of the substrate 1, the sensitivity is further improved.

In such a case, the alignment agent for the first 11 body, the second alignment agent, is for water 11 alignment, and the alignment agent for the second base body is for vertical alignment.
If so.

The following alignment agents are suitable for kf.

1) Solution application (physical adsorption) (1) @ Direct alignment lecithyl stearic acid, CTAB (hexadecyltrimethylammonium bromide).

Octadecylamine high j, low σ ride, etc. (2) iI
L-row orientation oriented carbon, polyexyethylene, 8-samide 125, polyvinyl alcohol, polyimide, etc. 1) Solution coating (chemical adsorption) (1) Vertically aligned monobasic carboxylic acid chromium complex (e.g. myristic chromium complex, perfluorononane acid complex), organic silane (e.g. DMOAP), etc. (2) Parallel oriented two-layer carbon-based carbon chromium complex (e.g. brassyl chromium complex), organic silane (e.g. MAP), etc. 3) Plasma polymerization (1) Vertically aligned hexamethyldisiloxane, perfluorodimethylcyclohexane, tetrafluoroethylene, etc. (2) Parallel aligned acetylene, etc. 4) Sputtering (1) Vertically aligned polytetrafluoroethylene, etc. 5) Liquid crystal dissolution injection (physical adsorption) (1) Vertically aligned lecithin, CTAB, persamide 100. Otadecylmalon resistance (2) Parallel oriented knee basic fatty acid (Example: ) 100G (CH2) ncO
OH, n = 3 to 11), / Hesami F' 125, crown ether, etc., and other necessary materials.
Orient in 7 rows.

2) 'Oblique Vapor Deposition Method (1) - Heavy Vapor Deposition An oxide such as SiO is deposited from an oblique angle and is oriented obliquely parallel (shallow evaporation angle) or parallel (deep evaporation angle).

(2) On the double evaporation surface, the first layer of an oxide such as SiO is evaporated at a shallow evaporation angle, and the second layer is evaporated at a deep evaporation angle by rotating the substrate surface by 90 degrees, and the oxide is oriented parallel to the slant.

(3) While rotating the rotary evaporation surface, oxides such as SiO are evaporated from different angles and oriented vertically.

3)' Irradiate the slope of the ion beam from an oblique angle and etch the ion beam.
Orient parallel.

4) 'Plasma method 1n1 is etched using element-resistant plasma or the like and oriented in parallel.

5) ``Pull-up coating'' Ill1j method Immerse the substrate in a solution such as polymer, and apply 4+ l
, , parallel orientation, etc. may be performed.

Note that it is preferable that a groove for tracking is provided on the surface of the first base.

In this case, the grooves may be concave or convex.

Further, the shape thereof may preferably be square, semicircular, semielliptical, 7-shaped, etc., or may have no corners, and may be selected from various shapes depending on the alignment characteristics of the liquid crystal material.

Furthermore, a heat insulating layer may be provided on the ``electrode layer'' 2 of the first base.

Further, a reflective layer or a semi-transparent reflective layer may be provided on the first substrate.

IV. Specific Effects of the Invention The body of the present invention irradiates laser light intensity from the transparent or semi-transparent substrate side. Due to this.

Smectin-ku-nematic transition, smectin-ku-nematic transition, or smectin-ku-nematic isotropic transition occurs in response to the irradiation beam.
A recording point is formed.

Reading of recording points is performed by detecting reflected light or transmitted light, usually reflected light.

In order to partially erase the area, for example, an erasing laser beam may be irradiated while applying an electric field.

Further, in order to erase the entire area, it is sufficient to heat the entire area while applying an electric field or to irradiate erasing light.

In addition, writing may be performed while applying an electric field, or erasing may be performed by heating without applying a voltage.

Furthermore, erasure may be performed by changing the laser pulse width, laser spot shape, or laser light intensity.

(2) Specific Effects of the Invention According to the present invention, since indolenine dyes are used among cyanine dyes, recording sensitivity is significantly improved.

Furthermore, the read S/N ratio is also improved.

Furthermore, erasure deterioration and reproduction deterioration in recording sensitivity and read SIN ratio are significantly reduced.

The present inventors conducted various experiments to confirm the effects of the present invention. An example is shown below.

Experimental Example Glass (ITO was coated on a plate to serve as the first and second substrates.Also, on the electrodes of the IL substrate, AI
An L reflective layer was laminated.

Both substrates were integrated with an inter-electrode spacing of 8 gm, and a smectic liquid crystal mixture 32 (manufactured by British Dry House Co., Ltd., etc.) was housed inside to obtain samples 1 to 6.

In this case, the liquid crystal contains the above-mentioned cyanine dye and the above-mentioned quencher in a molar ratio of 5:2.
% was included.

Furthermore, in samples Nos. 3 and 4, the first layer (electrode layer of ITO) consisted of the cyanine dye and the above-mentioned quencher (layer ratio 2:1) of 0.1 μm.
Sample No.
I got 7 and 8.

In addition, in sample No. 7.8, the l of the first substrate
<-After coating the acrylic photopolymer on the -7 talocyanine layer on the pear blade and curing it with light, KHM403
A horizontal alignment agent (manufactured by Shin-Etsu Chemical Co., Ltd.) was formed at a thickness of 500 mm, and a vertical alignment agent of FS-150 (manufactured by Dainippon Ink Co., Ltd.) was formed at a thickness of 600 mm on the ITO layer of the second substrate. The sample was formed and the result was 9.10.

For each of these samples, writing was performed from the transparent electrode side using a GaA1As laser as a light source and a condenser output of 15 mW.

Next, GaA1As laser (condenser output 0, 8
mW) as the readout light, the S/N ratio of the reflected light is 50d.
The writing light pulse width corresponding to B was measured, and the reciprocal of the sensitivity was calculated.

In addition, writing was performed using the write light of 200 n sec pulse +11, then reading was performed using the read light, and the read S/N ratio was measured.

Furthermore, while applying an electric field of 30 V, GaAiA s
Laser irradiation was performed, erasing and rewriting were performed five times, and the subsequent deterioration of the S/N ratio was measured.

The results are shown in Table 1.

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

Applicant: TDC Co., Ltd. Agent Patent attorney: Yo Ishii - Continued from page 1 @ Inventor: Takahashi - Husband: Inventor: Nanba Head of office: 1-1, 1900, Nihonbashi, Chuo-ku, Tokyo Inside TDC Co., Ltd. TDC Co., Ltd., 1-1, 1-1, Nihonbashi, Chuo-ku, Tokyo

Claims (9)

[Claims] (1)' A base body with an electrode layer and a J with a transparent electrode layer
1. An optical recording medium having a recording layer containing a liquid crystal between it and a bright substrate, characterized in that the recording layer contains an indolenine cyanine dye and a quencher. (2) Indolenine-based cyanine dyes have the following formula:
1) The optical recording medium according to claim 1.・General formula (I) Φ-L=heavy (x-)Ill (In the above-mentioned general formula (I), Φ and ! are each an indolenine ring, a thiazole ring, or an oxazole ring to which an aromatic ring may be fused. , represents a selenazole ring, imidatool ring or pyridine ring,
At least one of Φ and ψ is an indolenine ring to which an aromatic ring may be fused, L represents a methine chain, X″″ represents an anion, and m is O or l. . ) (3) The optical recording medium according to claim 1 or 2, wherein the quencher is a chelated agate of a transition metal. (4) An optical recording medium having a recording layer containing a liquid crystal between a substrate having an electrode layer and a transparent substrate having a transparent electrode layer, wherein the recording layer includes an indolenine-based cyanine dye and a quencher; An optical recording medium characterized in that the electrode layer has a layer containing an indolenine cyanine dye and a quencher. (5), f-drenine-based cyanine dye has the following general formula (
The optical recording medium according to claim 4, which is indicated by I). In the general formula (I) Φ-L-%P (X-'')m (the above general formula CI), Φ and ! are each an indolenine ring, a thiazole ring, or an oxazur ring to which an aromatic ring may be fused. , represents a selenazole ring, imidazole ring or pyridine ring, but Φ
At least one of and ψ is an indorenine ring to which an aromatic ring may be fused, and L represents a methine chain. X- represents an anion; m is O or l. ) (6) The optical recording medium according to claim 4, item 1 or 5, wherein the quencher is a compound of Kire-1 of Sumikkin 74. (7) An optical recording medium having a recording layer containing a liquid crystal between a substrate having an electrode layer and a transparent substrate having a transparent polar layer, wherein the electrode layer contains an indolenine cyanine dye and a quencher. or the recording layer contains an indolenine cyanine dye and a quencher, and an alignment agent layer is provided on the electrode layer and/or the transparent electrode layer. Characteristic optical recording media. (8) The indolenine cyanine dye has the following general formula (
The optical recording medium according to claim 7, which is represented by I). General formula (I) Φ-L='l' (X-)m (In the above general formula (I), Φ and ψ are each an indolenine ring, a thiazole ring, or an oxazole ring to which an aromatic ring may be fused. , represents a selenazole ring, imidazole ring or pyridine ring, but Φ
and! At least one of them is an indolenine ring to which an aromatic ring may be fused, L represents a methine chain, X- represents an anion, and m is 0 or 1. ) (9) The optical recording medium according to claim 7 or 8, wherein the quencher is a transition metal chelate compound.