JPS60232995A - Optical recording medium - Google Patents

Abstract

PURPOSE:To enable to obtain a recording layer which is little deteriorated on reproduction and has favorable moisture resistance, by incorporating a bonded substance of a dye cation and a quencher anion as well as a dye. CONSTITUTION:A recording layer of the optical recording medium comprises a bonded substance of a dye cation and a quencher anion. Each of the cationic dye constituting the inonic bonded substance and a dye having a positive charge which is added separately from the cationic dye is a dye having a heterocyclic ring comprising a hetero atom or a dye comprising a methine chain and having a positive charge. With the dyes incorporated in the recording layer, writing sensitivity is high, and S/N ratio in reading is high. On the other hand, the quencher anion constituting the bonded substance is preferably an anion of a chelate compound of a transition metal, in view of the fact that deterioration on reproduction is reduced and the compatibility thereof with a dye-finding resin is favorable. Accordingly, since the recording layer is provided by adding a dye to an ionic bonded substance of a dye cation and a quencher anion, deterioration on reproduction by reading light is slight, and light resistance is favorable. In addition, light absorbance is enhanced, and reflectance is enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to a recording method for an optical recording medium, particularly a heat mode optical recording medium.

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out.

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require 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.

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 containing Te in the -F form.

However, in recent years, because Te-based materials are harmful, there is a need for higher sensitivity, and there is a need to lower manufacturing costs, organic materials mainly containing dyes have been used instead of Te-based materials. For example, for He-Ne lasers, there are an increasing number of proposals and reports on media using recording layers of the He-Ne laser.

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

Technol, +8 (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 a metal phthalocyanine dye for a semiconductor laser (No. 58-8871115).

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 medium production method [2.Te system].

However, the reflectance of a dye-deposited film to a laser is generally small, and the current conventional method of obtaining a readout signal by changing (reducing) the amount of reflected light due to pits cannot obtain a large S/N ratio.

In addition, if a transparent substrate supporting a recording layer is integrated with the recording layers facing each other in a so-called air sandwich structure, and reading and writing 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/reproducing method is also not possible with a dye-deposited film.

This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate).
In addition, the surface reflectance is relatively high (4%), and the reflectance through the substrate of the recording layer is about 60% or less for polymethyl methacrylate, for example, so it is difficult to detect a recording layer that exhibits only a low reflectance. Because you can't.

In order to improve the readout S/N ratio of a recording layer formed by a dye-deposited film, an anode is usually added between the substrate and the recording layer.
A vapor-deposited reflective film such as the following is interposed.

In this case, the reflective film is used to increase the reflectance and improve the S/N ratio, and the reflective film may be exposed due to focus 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 Japanese Patent Application Laid-Open No. 1890-1890, IR
-132 dye (manufactured by Kodak) and polyvinyl acetate;
, 1'-diethyl-2,2'-)lycarpocyanine iodide and nitrocellulose;
ys.

Lett, 39 (9) 718 (1981) describes a coating method for forming a recording layer consisting of a dye and a resin, such as a recording layer consisting of 3,3'-diethyl-12-7cetylthiatetracarpocyanine and polyvinyl acetate. A layered medium is disclosed.

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

In this way, recording and reproduction through the substrate is possible,
In order to realize a medium having a recording layer made of an organic material that is compatible with a medium having a recording layer made of a Te-based material, the organic material itself needs to exhibit a high reflectance.

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

It has been reported that vanadyl phthalocyanine membranes exhibit slightly high reflectance (P, Kivits, etal, Ap
pl, Phys,' Part A 28 (2)
101 (1881).

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

In addition, cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes have been reported [Yamamoto et al., Proceedings of the 27th Japan Society of Applied Physics, 1 p-p (1980)], and a proposal based on this was published in JP-A-Sho. 58-1127130
However, these dyes have low solubility in solvents, tend to crystallize, and are extremely unstable against readout light, resulting in immediate decolorization, especially when applied as a coating film, making them impractical for practical use. It cannot be offered to

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 a high PJS reflectance of 1. It is proposed to be used as a single layer film (
Patent Application No. 57-134397, No. 57-134170
issue).

Furthermore, in other cyanine dyes such as indolenine, thiazole, quinoline, and selenazole, long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization. (Japanese Patent Application No. 57-182589, No. 57-177778, etc.)

Furthermore, it has improved photostability, especially decolorization by readout light (
In order to prevent (reproduction deterioration), we have proposed adding a quencher consisting of a transition metal complex to cyanine dye (Patent Application No. 57-186832, No. 57-1).
No. 88048, etc.).

In addition, styryl-based, indolyl-based, biryllium, thiapyrylium, selenapyrylium or telllopyrylium-based, polymethine-based dyes are dyes that have a petero ring containing a positively charged hetero element, or dyes that have a positively charged methane chain. We have also proposed adding a quencher to reduce regeneration deterioration (Japanese Patent Application No. 1813-1983).
No. 67, No. 5B-181368, No. 58-1813H
No. 58-183454, No. 58-183455
No. 58-18345.8].

However, dyes with a petero ring containing a positively charged heteroatom, or a dye with a positively charged methine chain,
Usually has a counter-anion.

In addition, a mixture of quenchers consisting of transition metal complexes is
Since they usually have counter anions, the presence of these causes problems in moisture resistance.

Therefore, in order to improve moisture resistance and improve storage stability,
Proposal of a coating film using an equimolar ionic combination of a dye cation having a petro ring containing a positively charged heteroatom, or a dye cation having a positively charged methine chain, and a quencher anion made of a transition metal complex. (Patent Application No. 59-14848).

By the way, in an equimolar ionic combination of a dye cation and a transition metal complex quencher anion, the proportion of the dye becomes relatively small, and the dye per unit weight of the coating film is diluted, resulting in poor absorption and reflection as an optical recording medium. There are cases where the write sensitivity and read S/N ratio are not sufficient.

Furthermore, an equimolar ionic combination of a dye cation and a transition metal quencher anion generally has poor solubility and poor film-forming properties, and therefore there is a problem in that the S/N ratio cannot be changed to a sufficiently large value.

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 having a recording layer containing a dye that exhibits extremely little reproduction deterioration and has good moisture resistance. It's about doing.

Such objects are achieved by the invention described below.

That is, the present invention.

In an optical recording medium in which a recording layer is provided on a substrate J2,
The present invention is an optical recording medium characterized in that the recording layer contains a combination of a dye cation and a quencher anion, and further contains a dye.

■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 a combination of a dye cation and a quencher anion.

In this case, there is no restriction on the ionic valence of the dye cation and quencher anion, and various combinations are possible, but generally both are monovalent.

That is, when the dye cation is D+ and the quencher anion is Q-, the conjugate is usually D+φQ-.

The cation of the dye constituting the ionic bond in the present invention is not particularly limited, and various cations can be used.

However, when these various dyes are incorporated as cations into the recording layer, the writing sensitivity is high and the reading S
A compound having a high /N ratio is a cation of a dye having a heterocycle containing a positively charged heteroatom, or a cation of a dye having a positively charged methine chain.

In such a case, as the cation of a dye having a heterocycle containing a positively charged heteroatom, in particular, the following general formula C
Those represented by I) to (IV) are preferred.

General formula (I) Yl-1 -CiCH-CHζN"-R14 1: In the general formula (1), Z represents an atomic group necessary to form a fused benzene ring or a naphthalene ring, and R11 is , represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, and R12 represents a substituted or unsubstituted aryl group.

! , 1 and L2 each represent a 1M substituted or unsubstituted methine group, Ml is 1 or 2, and Yl is necessary to form a nitrogen-containing heterocycle.

m is 0 or 1, and R14 represents a substituted or unsubstituted alkyl group, aryl group, or alkenyl group.

]] In General Formula I], R11 and R14 bonded to the H atom of the nitrogen-containing ring at both ends may be the same or different, and each represents a substituted or unsubstituted furkyl group, an aryl group, or Represents an alkenyl group.

In this case, there is no particular restriction on the number of carbon atoms in these groups. Moreover, the alkyl group may be chain-like or cyclic.

When these groups are substituents, the substituents include a sulfo group, a carboxy group, a hydroxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an alkylamido group, an alkylsulfonamide F group, an alkyloxy group, Alkylamino group, alkylcarbamoyl 7
+(, alkylsulfamoyl group, arylcarbonyloxy group, aryloxycarbonyl group, arylamide group, arylsulfonami F group, aryloxy group,
Examples include an arylamino group, an arylcarbamoyl group, an arylsulfamoyl group, a halogen atom, and those in which one or more of these is substituted with the other.

Further, R12 bonded to the 2-position of the left-most indole ring or benzindole ring in general formula CI) is a substituted or unsubstituted aryl group (particularly a phenyl group).

In this case, examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and the like.

On the other hand, Z represents an atomic group necessary to form a fused benzene ring or a naphthalene ring, so that an indole or benzindole ring (α-
or β-, which may be the ρ isomer).

Further, other substituents may be bonded to predetermined positions in these rings.

Examples of such substituents include halogen atoms.

Alkyl group, aryl group, heterocyclic residue, alkoxy group,
aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy η group, alkylamide group, arylamide group, Alkylcarbamoyl group, arylcarbamoyl group, alkylamine group, arylamino group, carboxylic acid group, sulfonic acid group, arylcarbonyl group, arylsulfonyl group,
An alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, a nitro group, a hydroxy group, etc., or one or more of these groups are further substituted with other groups among them. There may be a variety of substituents, such as

Furthermore, a nitrogen-containing heterocycle completed by Yl is bonded to the right end of the methine chain. However, the methine chain and the N atom are located next to the carbon atom bonded to the methine chain with m=o, or are located next to the carbon atom bonded to the methine chain in the heterocycle with m=1 via dimethine. located.

In such a case, the right-most ring containing Yl may be any of various known nitrogen-containing heterocycles in cyanine dyes.

For example, thiazole ring, benzthiazole ring, naphthothiazole ring (α and β), thiadiazole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, selenazole ring, benzselenazole ring, naphthoselenazole ring, quinoline ring, pyrimidine ring , quinoxalici ring, quinazoline ring, phthalazine ring, quinoline ring, benzimidazole ring, indole ring (especially 3,3-dialkyl-2-indolenyl, etc.), naphthyridine ring, thiazolopyridine ring, thiazoloquinoline ring, oxazoloquinoline ring, pyrrolopyridine ring, etc.

A substituent similar to the indole ring or benzindole ring at the left end of 1- may be bonded to these rings.

Furthermore, Ll and L2 are methine groups which may have a substituent, but are usually CH.

Moreover, the methine chain formed by these may contain a ring in the middle.

Also, l, is, l or? It is.

Next, specific examples of the dye cation represented by general formula (1) will be given.

In the following, Φ is a ring containing Z at the left end, and among these, i represents an indole ring and bi represents a benzindole ring.

Also,! is a ring containing Y.

1, 1, 1, 1, - , - , - -, - - 1 ~ yen lie ■ トQ (J υ υ Q ~ LSJ evil 0 - - - :l: :l: 工 :e えE engineering υ o o u
u o υ −, −, −, −Jl)'J)ヱ一 --〜 J) J -力, , OJA'J ロ LJI-I- OQ LI Ll u W Acid anions of these dyes, e.g. CM- .

Br-, I-, ClO4-, CH3<'>503-.

The conjugate with C or C>303-, B Fs-, etc., is
If 1=1 or 2, US Pat. No. 3,815,810;
No. 3314798, No. 9505070, Special Publication No. 1972-20727, No. 5B-49343, No. 5B-
It is synthesized according to No. 14111, No. 582-1768, etc.

In addition, in the case of view = 2 and 3, J, Chemical
Society, 128B (1981), Berri
chte, 94.838 (1980), Bullet
in pf the Chemical 5ociet
7 of Japan, 43.1588 (1970)
After the methine chain is extended to form an α,β-unamicable aldehyde, it is synthesized according to method -1-2.

General formula (II) ”—in the general formula (II).

Y2 represents an atomic group necessary to complete the indolenyl group which may have a fused ring.

R21 represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, Ll and L2 each represent a substituted or unsubstituted methine group, and the intersection 2 is an integer of 1.2 or 3.

R22 represents a monovalent group.

k is 0 or an integer from 1 to 5. However, k is 2
In the above case, the plurality of R22s may be different from each other or may be the same.

In the above general formula (II), the ring completed by Y2 is preferably as shown below.

I! 12, [Φm) (R25) q "21 In the above general formula (II), R21 represents a substituted or unsubstituted alkyl group (for example, methyl, ethyl, butyl,
octyl, etc.), aryl groups (e.g. phenyl, etc.),
or alkenyl groups (e.g. allyl, metaallyl, etc.)
It is.

There is no particular restriction on the number of carbon atoms in R21.

In addition, when these are substituted, examples of the substituent include an alkylcarbonyloxy group, an alkylamide group, an alkylsulfonamide group, an alkoxycarbonyl group, an alkylamino group, an alkylcarhemoyl group, and an alkylsulfamoyl group. group, arylcarbonyloxy group, arylamide group, arylsulfonamide group, aryloxycarbonyl group, arylamino group, arylcarbamoyl group, arylsulfamoyl group, water group, carboxy group, sulfonic acid group, halogen atom, etc. It may be.

Further, in the formulas [Φ] to [Φ■], two substituents R23 and R24 are preferably bonded to the 3rd position. In this case, the two substituents R23 bonded to the 3-position,
R24 is preferably an alkyl group or an aryl group.

Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

Furthermore, other substituents R25 may be bonded to predetermined positions in these rings.

Such substituents include halogen atoms, alkyl groups, aryl groups, heterocyclic residues, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbonyl groups, and aryloxycarbonyl groups. group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamido group, arylamido group, alkylcarbamoyl group, arylcarbamoyl group, alkylamino group, arylamino S, carboxylic acid group, sulfonic acid group, alkylsulfonyl group, Various substituents may be used, such as an arylsulfonyl group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, a nitro group, and a hydrococonut group.

The number of these substituents (p, q, r) is usually
It is assumed to be 0 or about 1 to 4.

Note that when p, q, and r are 2 or more, the plurality of R25s may be different from each other.

L, , L2 are methine groups which may be substituted as described above, but are usually CH.

The methine chain formed by these may contain a ring in the middle.

The intersection 2 may be either 1.2 or 3.

R22 represents a monovalent group, 20,1°2.3.4
Or 5. In this case, when k≧2, the plurality of R22s may be the same or different in the bud.

Note that k is 1-1 or more, especially l or 2, one of which is bonded to the p-position, the other one is bonded to the m-position, and R22 bonded to the p-position is 0 is preferably a substituted or unsubstituted dialkylamino group or alkyloxy group; examples of the substituent in this case include a sulfonic acid group, a cyano group, an I\rogen atom, a carboxylic acid group, etc. .

Next, specific examples of the dye cation represented by the general formula (IT) will be given.

- ~ 0 sun ri ■ ω ■ □ □book ;I
= = Ro ox = = = = = When l = 1 or 2, such a conjugate of a dye cation with an acid anion is disclosed in Japanese Patent Publication No. 31-5920 Gin, U.S. Patent Nos. 1845404 and 3852283, It is synthesized according to fJS33B4487, Japanese Patent Publication No. 57-4111058, etc.

Also, in the case of sentences = 2 and 3, J, Chemical
Society, 12H (19B+), Berich
te, 94.838 (19B+), Bulletin
of the Che+5ical 5ociety
of Japan, 43.1588 (1970), the methine chain is extended to form an α,β-unsaturated aldehyde, and then it is synthesized according to the 1-coordination method.

In the above general formula (m), R31 and R32 each represent an alkyl group, an aryl group, an added indolizine group or an indolizinium group, or a polystyryl group having a combination thereof.

R33 represents a monovalent group as described in JP-A-58-1711114, which constitutes an organic chromophore together with the indolizinone nucleus.

R34 represents hydrogen, an alkyl group, a cyano group, an acyl group, a carbalkoxy group, an aminocarbonyl group, an acyloxy group, or a halogen.

R35 represents hydrogen, halogen or an alkyl group.

Such a conjugate of a dye cation and an acid anion can be easily synthesized as described in JP-A-58-17164.

Representative examples of these dye cations are listed below.

In addition, in the following, φ represents a phenyl group.

D+kawa D"1l12 D+ll13 H3Cct-t3 \ , / D=III4 D"m5 R'R" r+now u++e () N (CH3)2 CH30
4) D” 11!+7 <> N (CH3) 2 t
-C489<)R'R'' ], in the general formula (IV), R41, R43 and R45 are each a hydrogen atom,
Represents a halogen atom, a substituted or unsubstituted alkyl group bonded directly or via a divalent linking group, an aryl group or a heterocyclic residue, or a group having a mono- or polymethine chain.

R42 and R44 each represent a hydrogen atom, a substituted or unsubstituted furkyl group, or an aryl group, and R42 and R43, or R44 and R45 are ? A fused ring may be formed by bonding to i=i, and X is 0. S
, Se or Te. .

That is, what is represented by the general formula (IV) includes pyrylium, thiapyrylium, selenapyrylium or telluropyryllium dye cations.

"-In the general formula (mV), R41, R43 and R45 may be the same or different, and each represents a hydrogen atom; a halogen atom: a direct or divalent linking group (-
0-, -N, H-, -NHR'- where R' is an alkyl group, aryl group, etc.) substituted or unsubstituted alkyl group, aryl group or heterocyclic residue: or mono- or polymethine chain represents a group having

Among such groups, the following are particularly preferred.

1) Hydrogen atom 2) Halogen atom 3) Substituted or unsubstituted alkyl group, aryl group, alkylaryl group, alkoxy group, aryloxy group, heterocyclic residue, or mono- or dialkylamide 7 group, etc.

In particular, tetrasubstituted or unsubstituted alkyl groups (methyl, ethyl, p-azinyl, etc.), substituted or non-Ha aryl groups (phenyl, p-N, N-dimethylaminophenyl, etc.), alkoxy groups (methoxy, ethoxy, etc.) ), aryloxy groups (fe/·xy, etc.), etc.

4) A group having the following mono- or polymethine chain r)
(7CR'=CH" +nCH=A+(Here, At
is a monocyclic or polycyclic heterocyclic divalent residue, such as oxazolilidene, thiazolilidene, selenazolylidene, imidazolylidene, villanylidene, thiazolilidene, selenapyrylium, telluropyrylium, oxaneindrazinylidene, benzoxazolilidene, benzothiazolylidene Represents lydene, penzopyranylidene, penzothiapyranylidene, penzoselenapyranylidene, penzotelllopyranylidene, etc., and R' and R'' are hydrogen atoms, halogens, substituted or unsubstituted alkyl groups, or aryl groups. It is the basis.

n is an integer from θ to 3. ) i i ) (-CR" = CR'" +rlA2 [Here, A2 is a hydrogen atom, an alkyl group (methyl, ethyl, etc.), an alkoxy group (methoxy, ethoxy, etc.), an aryl group (phenyl, naphthyl, etc.), Substituted or unsubstituted amino groups (dimethylamino, etc.), dialkylaminoaryl groups (dimethylaminophenyl, etc.), monocyclic or polycyclic heterocyclic residues (oxacylyl, 8-julolidyl, thiazolyl, selenazolyl, imidazolyl, pyrylium) , thiapyrylium, selenapyrylium, telluropyrilium, pyridinyl, furanyl, thiophenyl, selenophenyl, tellurophenyl, oxaneinradazinyl, benzoxazolyl, benzothiazolyl, penzoselenaturil, penzopyryliumyl, penzothiapyryliumyl, pen R' and R'' are the same as above, and n is an integer of O to 2.] Furthermore, R42 and R44 may be the same or may be different, and each hydrogen atom: or the above R41, R43
, R45 represents a substituted or unsubstituted alkyl group or aryl group.

In such a case, R42 and R43, or R44 and 1
45 may be bonded to each other to form a monocyclic to polycyclic fused carbocycle having about 5 to 20 carbon atoms.

As the condensed carbocycle, a substituted or unsubstituted benzene ring is particularly suitable.

Furthermore, X is O, S, Se, or Te, and depending on each atom, a pyrylium-based, thiapyrylium-based, selenapyrylium-based, or telluropyryllium-based dye is formed.

Such acid anion conjugates of dyes are disclosed in Japanese Patent Application Laid-Open No. 58-3
No. 2878 and J, Org, Ches+, 4
7 275235-5239 (1982).

Next, specific examples of the dye represented by the above general formula (Ilr) will be given.

Note that in the following, Ph represents a phenyl group.

E: I8 E hi hi ≧ ≧ hi Ro Ro Ro Ro Ro 〆　[F]　--[F]　 Engineering = .

Engineering: e Engineering E E’: e Engineering Engineering: I: E E Engineering E E 1- 1- ← ← H ← H No To Ol) ■ B - ~ ≧ ≧ hi ≧ hi ≧ and RO RO RO RO RO RO RO ■　σ　■　■　■ Engineering = Engineering = :l: Engineering 0:= Engineering :I: E E E = Φ　Φ　ω　Φ　ω )-1-1-←H ■IkuΦN Hee hee hee hee hee Ro Ro Ro Ro Ro ■　■　■　h　 0: Engineering Engineering: e: e: e workman E E E E ■ of Φ ←)-)-0 co's ro - ~ Hee ≧ Hee Hee Hee Ro Ro Ro Ro Ro Is it okay? Engineering: I: Engineering U　U　u　υ :e :I:! Engineering C) CJ (JL) E E E E l'.

vl Confinement η Hehi ≧ Hiro Ro Lo Lokri's −−1 Work O18 Work f Work Work: I: E E E E = : I: Work = Work = Work oJ Φ Φ Φ Prison I/) η η I η To φ φ Lo - ~ ~ To cSJ ■ - ≧ ≧ Hi Hi Hi Hiro Lo Lo Lo Ro υ OQ Oυ Q Work Work = = Work WorkΦ Φ Φ Φ Φ Φ ← H[-I ← ← H Hi Hi Hi Hee Hi ≧ Ro Ro Ro Ro Ro Ro0: E E E E ω ω 0 Φ a+ Φ [-1) -11-I HF-+ ← Hi ≧ Hi ≧ Hi Hi Hi Lo Lo Lo Ro Loe E Engineering Country l- I l-I [-I ← :I::e E E E* Ro Ro Ro Ro Ro Φ Φ l-I H Furthermore, as a dye cation having a positively charged methine chain, the following general formula [v ] is preferred.

General formula (V) -1- In the general formula (V), R51 represents a hydrogen atom, an alkoxy group, or a substituted or unsubstituted amino group, and A, B and C are each a substituted or unsubstituted phenyl group. or represents an alkyl group, in which at least one of A, B and C is 0R51.

Ll and L2 represent a substituted or unsubstituted methine group, and i n is 1 or 2.

In the above general formula [V,], R51 represents a hydrogen atom, an alkoxy group, or a substituted or unsubstituted amino group.

In this case, the alkoxy group is preferably a lower alkoxy group such as methoxy or ethoxy.

Further, the amino group may be unsubstituted or monosubstituted, but preferably disubstituted. Particularly preferred are methyl, ethyl, and di-substituted amino groups having a substituted (halogen, etc.) or unsubstituted benzyl group.
stomach.

Among these, R51 is preferably an amine group.

Further, Ll and L2 represent substituted or unsubstituted methine groups as described above, but a carbon ring may be formed in the methine chain formed by these.

On the other hand, A, B and C each represent a substituted or unsubstituted phenyl group or alkyl group.

As the alkyl group, methyl and ethyl are preferred.

Moreover, as a phenyl group, the above-mentioned -1! >Other than R51,
It may be an 8-substituted phenyl group or a phenyl group substituted with halogen or the like.

However, 1 to 3 of A, B, and C are <)R5
Must be 1.

Furthermore, n is 1 or 2.

Next, specific examples of the polymethine dye cation represented by the above general formula (V) will be given.

G"VI D"V5 D+V6 D+VII D"VI2 D+VI3 D"V14 D+V17 D+VI8 D+VI9 D"V2O D" V21 D+V23 ]◆V29 )"V2O )+ V31 [)"V32 D+ V33 With Nion The conjugate is
J, Am, Chew, Soc, 803772-
3777 (19518), He5Lu, ChiIl
, Acta 24369E, JP-A No. 56-8149, No. 9, No. 58-181690''r!F, etc.

Each of these dye cations usually takes the form of a single rod, but
If necessary, it may be in the form of a polymer.

In this case, one polymer includes two or more molecules of dye cations, and may be a composite of these dye cations.

For example, a single or co-condensate of a J- dye cation having one or more functional group IZ such as -0H1-COOH, -303H, or a dialcohol, dicarboxylic acid or Its chloride, diamine,
There are cocondensation components such as di- or triisocyanates, jepoxy compounds, acid anhydrides, dihydrazides, diiminocarbonates, and cocondensation products with other dyes.

Alternatively, a dye cation having a functional group listed in L 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)
, shearates of titanium, zircon, aluminum, etc.

Furthermore, -OH group, -0COR group, and -COOR
One or more dye cations having at least one of the following groups (wherein R is a substituted or unsubstituted alkyl group or aryl group), or together with other spacer components or others. It is also possible to use the dye bonded by -COQ-7A' by transesterification with the dye.

In this case, the transesterification reaction is preferably carried out using an alkoxide such as titanium, zircon, or aluminum.

Additionally, the dye cations described above may be bound to a resin.

In such cases, a resin having a specific group is used, and 1
- Similarly to the case of the above polymer, a dye cation is linked to the side chain of the resin by condensation reaction, transesterification reaction, or crosslinking, if necessary, via a spacer component or the like.

On the other hand, various quencher anions can be used as the quencher anion constituting the conjugate, but in particular, quencher anions with reduced regeneration deterioration and good compatibility with the dye-binding resin can be used. In this case, the central metal is preferably Ni, Co, or Cu.

Preferably M n , P d , P etc., especially,
The following compounds are preferred.

1) A bisphenyldithiol system represented by the following formula, where R1 to R4 represent hydrogen, an alkyl group such as a methyl group or an ethyl group, a halogen atom such as C1, or an amino group such as a dimethylamino group or a diethylamide group. In the formula, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pti.

Furthermore, another ligand may be bonded to the J double of M.

Some examples of this kind include handwritten notes.

RI R234 B RM Q-11HHHHN1 Q-12HCH3HHN1 Q-1-3HCI CI HN1 Q-14CH3HHCH3N1 Q-151:R3CH3G)13 C83N1Q-11
1f HC sentence HHN1 Q-17CI CI CI C sentence NiQ, -18M
CI CI CJL N1Q-1-9HHHHC.

Q”-1-10HCH3CH3HC.

Q-1-11HCH3(:R3HN1 Q-1-12HN(OH3)2HHN1Q-1-+3
HN(CH3)2N((:R3)2HN iQ -1-
+4 HN(CH3)2 CH3HN iQ,'-1-
15HN(CH3)2Cl HN iQ-1-18HN
(C2H,5) 2 HHN +2) Bisdithio-α-dika represented by the following formula, where R5 to R8 represent a substituted or unsubstituted alkyl group or aryl group, and M is Ni, Co, Cu, Represents a transition metal atom such as Pd or Pt.

In the following description, ph is a phenyl group, φ is a 1,4-phenylene group, φ' is a 1,2-phenylene group, and benz is a compound formed by bonding adjacent groups on the ring to each other. This represents the formation of a benzene ring.

6 7 8 R2HRRM Q-2-1φN (CH3) 2 ph ΦN((J
3) 2ph N iQ"'2-2 ph ph ph
ph N1Q-2-3φN(C,,I5)2 ph φ
N(C2H5)2 ph Nr3) represented by the following formula, where M represents a transition metal atom.

Ql is represents.

M Moxibustion - Q-3-I Ni Q12 Q-3-2Ni Q12 Q-3-3COQI2 Q-3-4Cu Q"Q-3"5 Pd Qk' 4) Expressed by the following formula, where M is transition Represents a gold atom, 1 (11 A represents S, C (or CQ2, I2 11 12
15 18 represents COOR, CONR, R* or SO2R17, 3H to R17 each represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, Q2 is 50 or 6 to form a ring Represents the required atomic group.

M A Q”'4-I Ni 5 Q-4-2Ni S Q-4-4N i C(CN)2 Q-4-5N i C(CN)2 5) Q, -5 represented by the following formula -I Ni In addition, as described in Japanese Patent Application No. 127075/1982, Shidamono 6) Thiocatechol chelate system represented by the following formula, where M is a transition metal atom such as Ni, Co, Cu, Pd, Pt, etc. represents.

Further, the benzene ring may have a substituent.

7) Those represented by the following formula, where R18 represents a monovalent group, the number is 0 to 6, and M represents a transition metal atom.

8 Mouse-1-Fun Q, -7-I Ni H0 Q-7-2Ni CH31 8) Thiobisferrate 1 represented by the following formula, where M is the same as above, and R85 and R66 are
Represents an alkyl group.

65 66 RR’M Q-8-1t-C3H1□N1 Q-8-2t-C3H17C.

Among the quencher anions listed in J2, the phenylbisdithiol-based ones listed in [2] are most preferred. This is because reproduction deterioration due to read light is further reduced and light resistance is extremely high.

Next, specific examples of the conjugate used in the present invention will be given.

Di D+II Q-8-I D2 D+I2 Q-6-I D3 D+ I3 Q-5-2 D4 D+ I7 Q-7-I D5 D+111 Q-1~8 D6 o + 112 Q-7-1I D7 D ◆ 113 Q'-1-3 D8 D÷ 114 Q-1-3 D9 D" 115 Q-1-8 DIOD+ I IS Q-1-12 DIl D" 117 Q-1=8 D12 0" 118 Q-1-12 D13 D" I21 Q"' 1-8D14 D+
I22 Q-1-12 D15 D” I25, Q-1-12DIB D+
I26 Q-1-12 D17 D+ I27 Q-1-8 D18 D+I30 Q-1-8 0190◆ I31 Q-1-8 D20 D+II2 Q-8-1 D21 D" 113 Q-5-2 D22 D" 115 Q , -1-3 D23 D" 126 Q-1i2 D24 D" 117 Q-1-12 D25 D" 119 Q-1-8 02111'D"1llOQ"-1-8D27 D"
1111 Q-1-12D28 D"ml 'Q-8-
I D29 D"m3 Q-6-1 0300"m6 Q-1-8 D31 D"R15Q'-1-8 D32 D" ■1B, Q-1-12D33, D"
m1llll Q-1-+2D34 D” m24 Q
-1-8 D35 D"m25 Q-1-3 038D ten R28Q"'1-12 D37 D"lV2 Q-6-I D38 D" IV3 Q-1-8 D39 D" lV5 Q-1-12 D40 D "N9 Q-1-8 D41 D+ IVIOQ, -1-8 D42 D+IVII Q-1-8 043D" IVI5 Q-1-12 D44 D+ IVIOQ-1-3 D45 D+ IV24 Q-1-8 D46 D÷ IV29 Q -1-8 D4? D+ IV57 Q-1-3 048D" IV59 Q"-1-12D48 D"
rVBI Q-1-12D50 D” VI Q-1-
12 D51 D+ V4 Q-1-3 D52 D"VII Q'-1-8 D53 D+V13. Q-1-12 D54 D+ VI5 Q-1-12 D55 D" VI9 Q-1-+2 D58 D+V20 Q-1- 8 D57 D” V2OQ-1-8 J D58 D+V31 Q-1-8 0690+ V34 Q-1-3 080D+ V35 Q-1-3 Such a conjugate in the present invention is produced, for example, as follows. .

First, a cationic dye combined with an anion is prepared.

In this case, the anions (^n-) are I"-, Br
-, CIC)r, BFa.

CH3<>SO3-, C party 0803-, etc. may be used.

Such dyes are known and can be synthesized according to conventional methods as described above.

On the other hand, an anionic quencher bonded to a cation is prepared.

In this case, the cation (Cat") is particularly N"
Tetraalkylammoniums such as (CH3)4, N+(C4H!l)4 are preferred.

Incidentally, these quenches and chars are known and can be synthesized according to conventional methods. In this case, in particular, the above item l) is disclosed in Japanese Patent Application Laid-open No. 57-186832 and Japanese Patent Application No. 58-1830.
Synthesized according to No. 80 etc.

Next, equimolar amounts of these dyes and quenchers are dissolved in a polar organic solvent.

As the polar organic solvent used, N,N=nidimethylformamide is suitable.

Further, its concentration may be approximately 0.01 mol/l.

Thereafter, an aqueous solvent, particularly water, is added to this to cause double decomposition and to obtain a precipitate. The amount of wood to be added may be a large excess of 10 times or more.

In addition, the reaction temperature is preferably about room temperature to 90°C.

Next, the two liquid phases are separated and subjected to evaporation drying, which is repeated 2 to 3 times as necessary, and then recrystallized from DMF-ethanol or the like to obtain the conjugate of the present invention.

In addition to the above method, a neutral quencher cation intermediate may be dissolved in methylene chloride or the like, and an equimolar amount of the dye may be added thereto, concentrated, and recrystallized.

Alternatively, nickel may be oxidized to form an anionic salt while blowing air according to Japanese Patent Application No. 57-18111832.

A specific synthesis example of the conjugate of the present invention is disclosed in Japanese Patent Application No. 1983-
14848, etc.

The recording layer of the optical recording medium of the present invention also contains, in addition to the above-mentioned conjugate, a dye having a heterocycle containing a positively charged heteroatom, or a dye having a positively charged methine chain.

There are no particular limitations on the dye in the present invention, and various dyes can be used.

However, among these various dyes, those that have high writing sensitivity and high reading S/N ratio when incorporated in the R layer are dyes that have a heterocycle containing a positively charged heteroatom, Alternatively, it is a dye with a positively charged methine chain.

In such a case, dyes having a heterocycle containing a positively charged heteroatom are particularly selected from the following general formulas (I') to [
■'] are preferred.

General formula [I'] Yl ''+ 10'(C)l-CH7N''-R14・(X-) n In the above general formula [I'], Z, R11°R12, Ll
, L2, Ml, Yl, , m, and R14 are the same as in the general formula [I] already described.

X- represents an acid anion, and preferred examples thereof include:
I-, Br-, C9,04-.

BFn　-, CH3<>303-.

C9, -O303-, etc. can be mentioned.

n is 1, but if one charge is present at a location other than X-, n is O.

; □. , JZ-1-2 General formula [1.]-,,a. 6
Specific examples of dye cations are given below.

D") M D' ll D+II I- D'I2 D"I2 I- D'13 D+l3F D"I4 D"I4 1- D'I5 D"I5 C look 04- I)'I6 D+I6 I- D'I7 D+I7 I- D'I8D"l8F D' I9 D"I9 I- D' llOD ÷ I 10 I -D' Ill
D" 111+ I C intersection 04-D' 112 D"
112 C intersection O4-D' I13 D+ 113 C
Stand 04-D' II4 D" 114 C sentence 04 D'
115 D" 115 C sentence 04 D' IIS D
+ 118 C 04-D' 117 D+ It?
I- D"l-180" 118 I- D' 119 D" 119 C view o4-D' I20
D"I2OCviewo4-D'I21' D+I
21 C sentence Oll -〇' I22 D" I22
C sentence 04-D' 123 D” 123 C sentence on-
D' I24 D" 124 C intersection 04 -D' I
25 D" I25 C or 0a-D' 128 D"
126 Cli 0a-D' 127 D" 127
C sentence 04-D' 128 D+ I28 C sentence 04
-D' ■ 29 D" 129 Cl0a -D'
130 D" 13D Cdan 04-D' 131 D
"131 1- D' I32 D+ I32 C or 04-D' I
33 D+ I33 C sentence 04-these pigment sentences=1
or 2, U.S. Pat. No. 3,815,610, U.S. Pat.
No. 314798, No. 3505070, Special Publication No. 1977-
No. 20727, No. 5fi-49343, No. 58-14
No. 111, No. 5B-1788, etc.

In addition, in the case of sentences = 2 and 3, J, ChemicalS
ociety, 128B (111181), Ber
ichte, 94.838 (+960), Bulle
tin pf the Chemical 5ocie
ty6f Japan, 43.1588 (fll1
70), the methine chain is extended to form an α,β-unsaturated aldehyde, which is then synthesized according to the above method.

General formula (II') ■ In the general formula (II''), Y2.R21°Ll
, L2. See 2. Regarding R21, R22, R23, R24°R25,k, the general formula [I! ] is the same.

X- represents an acid anion. Preferred examples thereof include I-, Br-, and ClO4-.

BF4-, CH34! > SO3-.

Examples include Cl　-O3O3-.

n is l, but if one charge is present at a location other than X-, n is O.

D+ x- D-111D◆ III ClO4- D"' II2 D" 112 C! lOs-D-1
13I)" 113 C9,04-D-114D"l1
4 C Immuno4- D-115D÷ II 5 C or 04-D-II6 D
"llB Cmata04- D-117D+IT7 ClO4- D'-II8 D+118 Cmata04-D-II9 D
+IIQ C party on- D-1 Summer 10 D” 1110 C to LO4-D-I
lll D+l111 I- D-l112 D" 1112 ClO4-D-111
3D◆ 1113 C view o4-D-1114D+111
4 ClO4-D-1115, D+ll15 C or 04
-D-1118D" ll1e C Oa-Such a dye is
No., U.S. Patent No. 1845404, U.S. Patent No. H522111
No. 3, No. 3384487, Special Publication No. 57-48056
Synthesized according to No. 1, etc.

In addition, in the case of sentences = 2 and 3, J, ChemicalS
ociety, 128B (1981), Beric
hte, 94.838 (1θ60), Bullet
in pf the Chemical 5ociet
yof Japan, 43.1588 (1970)
After extending the methine chain to form an α,β-unsaturated aldehyde, it is synthesized according to the method described above.

General formula [m'] In the above general formula [m'], R31, R32゜R33
, R34, and R35 are already mentioned (III)
It is similar to

X- represents an acid anion, preferred examples thereof being I-, Br-, ClO4-.

BFs　-, CH3(>　SO3-.

Examples include C-0503-.

n is l, but n is 0 if there is one charge at a location other than X-.

Such dyes are easily synthesized as described in JP-A-58-17184.

Next, specific examples of the dye represented by the general formula [■-] will be given.

D + ) M D-III D" III CF3 303 -D
−■ 2 D” II [2CF3 SO3-D'-m3
D" ■ 3 CF3 503 -D-m4 1)"
■4 CF3 303 -D-I [[50÷ [I5
BFa- D-mB D+lll6 I- D-m7 D"lll7 I- D -mB D 10 [8I- D-[9D" m 9 - CF3 503 -D-m
10 D”IIIOBF4-D-mll D” [
11BF4- D-m'12 D 10 m12 CF3 SO3-D"
-m13 D” [13CIO4-D-m14 D”
m14 8F4- D-l15. 0” l15 CF3 S 03-D
-m16 D÷II [lB BF4-D-m17 D”
I[[17BFa -D"' m18 D", 1I1
18 B Fa -D-m19 D÷Old 9 BFa- D-m20 D” ■20 CF3 S 03'-D
-m21 D◆ m21 BF4- D-II [22D” m22, CF3 303 -
D-n123 D" m23. B F4-D-m24
, D"m24 BFa-D'-m25 D+m25
CF35O3-D-llll2B D”llll2B
CF3 SO3 - General formula [■'] "-2 = General formula [■'], Y,, R41゜R42
, R43, R44, and R45 are the same as those in general formula (IV) described above.

X- represents an acid anion, preferred examples thereof being I-, Br-, Cl0a-.

υ BF4-, CH3-C>303-.

CJI-0303- and the like can be mentioned.

n is 1, but n is 0 if there is one charge at a location other than X-.

Such dyes are described in JP-A-58-3287111 and J. Oeg, Chew, 47275235-5.
239 (1982) etc.

Next 1. Specific examples of the dye represented by the above general formula [■'] are given below.

D"X- D' lVI D"lVI C104-D' IV2
D" ■2 8F4 -D' IV3 Dx ■3 C
F3 503 -D' IV4 D” IV4 BF4
-D" IV5 D" IV5 Cl0q -D'
IV6 D" IV6 ClO4-D' IV7 D"
IV7 CF3 SO3-D' IV8 D" IV
8 BF4 -D' IV9 D” IV9 BF4
-D'1VIOD"1VIOBF4-D'IVIID" IVII BFs -D'IV1
2 0" ■12 8F4 -D' lVI3 0"
IV13 BFs -D'IV14 D" 1VI4
BF4 -D'IVI5 D'' IV15 BF4 -
D' lVI6 D" rVlB BF, 1 -D'
1V17 D" IVI? ClO4-D' lVI8
D" lVI8 8F4 -D'[V2OD"1V
19 BF4-D'lV2OD" 1V20 B F4
-D' 1V21 D" IV21 ClO4-D'
IV22 'D' IV22 C9,04-D'IV
23 D" 1V23 CfLOi+ -D' ff2
4 D" 1V24 Cff104 -D' 1V25
D" 1V25 ClO4-D' IV26 D"
IV2B C intersection 04-D' lV2? D"IV27
ClO4-D′ IV28 D” IV28 ClO
4-D' 1V29 D" IV29 ClO4-D'
IV30 D" IV30 ClO4-D' IV3
1 D+ IV31 C sentence 04-D'IV32 D"
IV32 C sentence o4 -D' 1V33 D” IV3
3 C intersection 04-D' 1V34 D" ICl3 CF
3 S 03 -D'IV35, D"IV35
Cl0i+ -D' IV38 D” IV3B CF
3 S 03 -D' IV3? D"IV37C
F3 So3-D' IV38 D" IV38 B
F4-D' IV39 D” IV39 C O4-
D' rV40 D medium IV40 CF3 so3-D
'IV41 D" Ill CF3 s, o3-D'
1V42 D" IV42- BF4 -D' 1V
43 D" IV43 ClO4-D' IV44 D
"IV44 ClO4-D' IV45 D" IV
45 CfLO4-D' IV46 D" 1V4B
PFs −D′ 1V17 D”1V47 CF35O
3-D'IV48 D" IV48 CF3 S 03
-D' IV49 D" IV49 B F4-D'
IV50D" IV50 B F4 -D' [VS2
D 10 ■51 PFa -D' [V52 D” I
V52 CF3 S 03 -D'IV53 D"I
V53 CF3 S 03 -D'IV54 D” ■
54 CF3 S 03 -D'IV55 D"IV
55 CF3 S 03 -D' l758 D” I
V5B CF3 S 03-η D' IV57 D" IV57 CQO4-D' [
V2OD+rV58 CJJO4-D' IV59 D
"IV59 C!lO4-D' 1V6Q D"1V
80 ClO4−D′IV6+D”rVfilCQ04
-D′ IVEt2 D” IV62 CQOs -D
' 1V63 D"1V83 Cu04 General ° type [V
' ] In the general formula [V'], R51, A, B and C are the same as in the general formula (V) already described.

X- represents an acid anion. Preferred examples thereof include I-, Br-, and ClO4-.

BF4-, CH3 (>303-.

Cl-<>303-'i can be mentioned.

n is l, but n is 0 if there is one charge at a location other than X-.

Next, in the general formula [V'], J
j, improve body f column.

D" ) M D' VI D" VI CQOq -D'V2D"V
2C104- D' V3 D" V3 CQOs -D' V4 D
"V4 CQO4- D' V5 D" V5 CQO4- r)' V6 D" V6 CQO4-D' V7 D
"V7 Cl04- D'V8D"V8CIOq- D' V9 D"V9 Ccross04- D'VIOD" VIOCl04- D'VllD"VlIC, u04- D' VI2 D" VI2 CQOs -D' V
I3 D+ VI3 C1-D' VI4 0” VI
4 C104-D' VI5 D” VI5 Cl04
-D' VI6 D'' VI8 PFs -D' VI
7 D" VI7 ClO4-D' VI8 D+ V
I8 C904-D' VI9 D” VI9 CQO
4-D'V2OD"V2OC9,04-D'V2!
D"V21CgLOs-D'V22DV22CQOs-D'V23D"V23CJljO,-D' V24 D" V24 (1104-D' V2
5 D" V25 CJJO4-D'V2OD" V
2Ccuo4- D'V2? D+V27Cf04- D' V28 D ◆ V28 C cross 04-D' V
2OD"V2OCJJO4-D'V2OD" V2
OCQO, - D'V31D+V31CIO4- D'V32 D"V32 CuO4-D'V
33 D" V33 (, QO4-D' V34 D"
V34 CQO, -D ′ V35 D” V35
C1o 4 - Such dyes are J, Am, Che
w, Sac, 803772-3777 (+958
), Heuu, ChiIl, Actaha3Ei9
E, Japanese Patent Application Publication No. 58-181811, No. 58-181811.
Synthesized according to No. 09. ``Each of these dyes usually takes the form of a monomer, or if necessary, may take the form of a polymer.

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

For example, single or co-condensate of the above dye cations having one or more functional groups such as -OH, -COOH, -303H and the like.

Or these together with dialcohols, dicarboxylic acids or their chlorides, diamines, di- or triisocyanates,
There are co-condensed components (such as jepoxy compounds, acid anhydrides, shihedradit, diominocarbonate, etc.) and co-condensates with other dyes.

Alternatively, one dye having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dyes.

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, amine alcohols, enols) those with active hydrogen compounds, etc. as ligands)
, titanium, zircon, aluminum, etc.

The grains include -, OH, -0COR groups, and -COOH
One or more types of dyes having at least one group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or together with other spacer components or other dyes It is also possible to use a compound in which the compound is bonded through a -COO- group by a transesterification reaction.

In this case, the transesterification reaction is preferably carried out using an alkoxide such as titanium, zircon, or aluminum as a catalyst.

Additionally, the above dyes may be bound to a resin.

In such 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. The dyes are linked via a corresponding spacer component or the like.

The content of such a conjugate is 10 to 80 wt%, preferably 30 to 60 wt%.

If the amount of the combined body exceeds 80 wt %, the light control degree and reflectance of the optical recording medium will decrease. Also, t-1 compatibility deteriorates and film formability deteriorates, resulting in a small SZN ratio and deterioration in sensitivity.

If the amount of the conjugate is less than 10 wt%, the content of the conjugate will decrease, resulting in regeneration deterioration.

Further, unnecessary counteranions are present in the recording layer, which causes hydrolysis and tends to produce acids, alkalis, etc., resulting in poor moisture resistance.

Note that, if necessary, two or more of the binder and the dye may be contained.

A mixture of such a binder and a dye may be combined with other dyes to form a recording layer within a range that does not impair the effects of the present invention.

The recording layer may contain a resin if necessary.

The resin used is self-oxidizing, depolymerizing, or thermally O
f plastic resin is suitable.

Among these, M +i which can be particularly preferably used
) Plastic resins include the following.

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

11) Polyolefin copolymer For example, ethylene-vinyl acetate copolymer.

Ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-synthetic maleic acid copolymer, ethylene propylene terpolymer (IMF
T) etc.

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

1ii) Vinyl chloride copolymers, such as vinyl acetate-vinyl chloride copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-maleic anhydride copolymers, acrylic esters or methacrylic esters, and vinyl chloride copolymer, acrylonitrile-vinyl chloride copolymer, vinyl chloride 7r Jl/
8 Polymer, ethylene or propylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer graft-polymerized with vinyl chloride, etc.

In this case, the copolymerization ratio can be arbitrary.

1) Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadimone-vinyl halokenide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

M) Polystyrene M1) Styrene copolymer For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (3MA resin), Styrene-acrylic acid ester-acrylamide copolymer, styrene-butadiene copolymer (
SBR), styrene-vinylidene chloride copolymer, styrene-methyl methacrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

M11) Styrene-type multilayer bodies, e.g. α-methylpolystyrene, p-methylstyrene, 2
, 5-dichlorostyrene, α.

β-hinylnaphthalene, α-hinylpyridine, acenaphthene, vinylanthracene, or a copolymer thereof, such as a copolymer of α-methylstyrene/methacrylic acid ester.

M1ii) Coumaron-Inten resin Coumarone-indene-styrene copolymer.

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

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

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

Mata, R20 may be a substituted or unsubstituted alkyl group, but it is preferable that the number of carbon atoms in the alkyl group is 1 to B, and when R20 is a substituted alkyl group, the alkyl group The substituent for substituting is a hydroxyl group,
It is preferably a halogen atom or amino X (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, the atomic group represented by the above formula is Alternatively, an acrylic resin is formed by forming a homopolymer or copolymer having two or more repeating units.

Wing 1) Polyacrylonitrile Wing 11) Acrylonitrile copolymer For example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer Polymer, acrylonitrile-methacrylic ugly methyl copolymer,
Acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

! Item i) Dia7ton Acrylamide Polymer 7 Dia7ton acrylamide polymer made by reacting acetone with acrylonitrile.

! iMa) Polyvinyl acetate! m) Vinyl acetate copolymers, such as copolymers with acrylic esters, vinyl ethers, ethylene, vinyl chloride, etc.

The copolymerization ratio may be arbitrary.

! M1) Polyvinyl ether, such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc.

XMa11) Polyamide In this case, the polyamide includes ordinary homonylon such as nylon 6, nylon 6-6, nylon 6-10, nylon 6-12, nylon 9, nylon 11, nylon 12, nylon 13, etc. Nine 6/6-6
/ 8-10, nylon 6/6-6/12, nylon 6
A polymer such as /6-6/l 1 or modified nylon may be used depending on the case.

Tomi! 0 polyesters such as oxalic acid, succinic acid, maleic acid, adipikari 1
Condensates of various dibasic acids such as aliphatic dibasic acids such as cepasthenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, and glycols such as ethylene glycol, tetramethylene glycol, and hexamethylene glycol. Among these, condensates of aliphatic dibasic acids and glycols, and cocondensates of glycols and aliphatic basic acids are preferred. Particularly suitable.

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

! Polyvinyl acetal resins Polyvinyl formals and polyvinyl acetal resins obtained by acetalizing polyvinyl alcohol are both preferably used.

In this case, the degree of acetalization of the polyvinyl acetal resin can be arbitrary.

! polyurethane resin Thermal H with urethane bonds (plastic polyurethane resin).

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

! Violet 1) Polyether styrene formalin resin, cyclic aceter) Ring-opening polymer of V, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc.

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

Polycarbonates - Various polycarbonates such as polydioxydiphenylmethane carbonate and dioxydiphenylprobancarbonate.

Violet! lma) Ionomer Sodium such as methacrylic acid and acrylic acid.

Li, Zn, Mg salts, etc.

Xπma) Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetophenone and formaldehyde.

+ x'x 1) Xylene resin, for example, a condensate of m-xylene or mesitylene and the present lumaline, or a modified product thereof.

! ! ii) Petroleum shelf C5 series, C9 series, C3-CqJt' polymerization series, dicyclopentadiene series, or Kawaaki combinations or modified products thereof.

i! V item 1) Above I)~! A blend of two or more types of violet lily, or a blend with other thermoplastic shelves.

In addition, the molecular weight etc. of resin may be various.

Such 4#l fat and the above-mentioned conjugate are usually applied in a wide range of quantitative ratio of 0.1 to 100.

Incidentally, such a recording layer may additionally contain other quenchers 1, such as those described in Japanese Patent Application No. 181388/1988, etc., if necessary.

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 H layer is usually about 0.03 to 10 μm.

In addition, such a recording layer may contain other dyes, other polymers or oligomers, and various rfrq! A surfactant, an antistatic agent, a lubricant, a flame retardant, a stabilizer, a dispersant, an antioxidant, a crosslinking agent, and the like may be contained.

To form such a recording layer, it is sufficient to apply it onto the substrate using a prescribed melt and dry it.

Examples of melts used for coating include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, and ethers such as methyl cellosolve and ethyl cellosolve. or aromatic systems such as toluene and xylene.

Alkyl halides such as dichloroethane, alcohols, etc. 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 base body usually has a groove for troughing.

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

In order to improve solvent resistance, wettability, surface tension, thermal conductivity, etc., it is preferable to form a base layer on these substrates. The material of the base layer is Si,
Ti', A1. Z'r, In, N i, T a
11 organic complex compounds and organic polyfunctional compounds such as! Preferably, the material is an oxide formed by drying cloth or heating.

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

In addition, various top protective layers,
It is also possible to provide a single layer of half-mirror. however,
It is preferable that the recording layer is a single layer film and that one reflective layer is not provided at -L or aWL below the recording layer.

The medium of the present invention may have a recording layer (1) on one side of such a substrate, or may have recording layers on both sides 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, and they are sealed tightly to prevent dust and scratches. You can also do it like this.

(2) Specific Effects of the Invention The medium of the present invention irradiates recording light in a pulsed manner while running 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.

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

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

(2) Specific Effects of the Invention According to the present invention, the absorbance as an optical recording medium increases and the reflectance increases.

Since the solubility is good and the film forming property is good, an optical recording body with good writing sensitivity and a good reading S/N ratio can be obtained.

In this case, in the present invention, since the dye is added to the ionic combination of the dye cation and the quencher anion, the reproduction deterioration due to the readout light is smaller than that of a mixture of the dye and the quencher, and the light resistance is also good, so the characteristics deteriorate when stored in a bright room. Less is.

Furthermore, the absorbance is higher and the reflectance is higher than that of a recording medium made only of a bond.

Therefore, writing and reading can be performed satisfactorily through the substrate without providing a reflective layer.

It also has good solubility and little crystallization.

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

Example 1 The conjugate and dye D' shown in Table 1 below were dissolved in a predetermined solvent in the proportions shown in Table 1, and silicone colloid IK liquid [Colcoat 108X, (manufactured by Colcoat)] was prepared. An acrylic disk substrate with a diameter of 30 cm on which a base layer (0, 01 diameter) was provided by applying and hydrolyzing 0.
Various media were obtained by coating to a thickness of 0.06 final layer.

In this case, in Table 1, NC has a nitrogen content of 11.5 to
12.2%, viscosity 80 based on JIS K 8703
Second nitrocellulose, its content is 10wt%
It is.

Separately, for comparison, we prepared a medium consisting only of a combination of a single dye cation and a Kuncher anion, a medium containing only one element, and a verchlorate of D''I21 (D'I21).
, and tetrabutylammonium salt of Q-1-8 (Q
A medium containing a mixture of 1-8) was prepared.

In addition, while the dyes used were exemplified in Gyokuki, the ones used later were used.

Furthermore, Table 1 shows the respective weight ratios of the conjugate 1 dye and quencher.

Writing was performed on each medium thus produced from the back side of the substrate using a semiconductor laser (830 nm) or a He-Ne1z laser while rotating at 900 rpm.

Each medium was irradiated with write light with a different pulse width, and the pulse width that changed the extinction ratio by 2.0 was measured, and the reciprocal of the pulse width was taken as the write sensitivity.

In addition, writing was performed using a condensing section output of 10 W and a frequency of 2 MHz, and then a semiconductor laser (830 nm, condensing section output of 1 W) was used as read light, and the reflected light through the substrate was detected to detect the error. Spectrum analyzer unit manufactured by Ulett Paracard, Band IIJ30KHz unit S
/N ratio was measured.

In addition, 1 mW laser readout light was applied for 1 Bsec11.
Reproduction deterioration was evaluated by measuring the change (%) in reflectance from the back side of the substrate after irradiating it as a 3 KHz pulse for 5 minutes in a static +l- state.

These results are shown in Table 2.

From the results shown in Table 2, the effects of the present invention are clear.

That is, according to the present invention, reproduction deterioration is significantly reduced compared to when a normal dye is used alone. Also, compared to using a mixture of a dye and a quencher,
Alternatively, compared to using the conjugate alone, C/N
The ratio is more than 3 dB.

Continuing from page 1 ■Int, CI,' Identification symbol Internal reference number G 11
C131047341-5B@Inventor Takahashi
- Husband, Tokyo Chuo Type 1 Company Inventor: Akihiko Kuroiwa, Tokyo Chuo Type 1 Company

Claims (1)

[Claims] l) An optical recording medium comprising a recording layer formed on a substrate, wherein the recording layer contains a combination of a dye cation and a quencher anion, and further contains a dye.