JPS59229396A - Photo-recording medium - Google Patents

Abstract

PURPOSE:To reduce deterioration of a S/N ratio at a time of high-temperature preservation in a photo-recording medium provided with a recording layer containing light-absorbing substance, by employing as a light-absorbing substance, a dye-polymer connected with a connecting radical containing-COO-radical to more than one dye molecule. CONSTITUTION:A dye-polymer which connects more than two dye molecules of one or more than two kinds by a -COO-radical or more than 2 radicals of valence of more than 2 is used as a light-absorbing substance in a recording layer. The dye demands no special limitation and RCOO-radical and R'OCO-radical in the molecule are converted by ester between, for instance, molecules of the same kind and connection is mode with the -COO-radical. For a connecting radical containing more than two -COO-radicals, a radical represented in formulae (X)-(L)n is preferable (where L stands for O, CO or COO, n integer larger than one, X residual radical of 2-3 valence). This kind of light-absorbing substance may construct the recording layer as a composition that contains resin, quenching agent, etc.

Description

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

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

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. Some devices perform writing by forming small holes, record information using the pits, and read out information by detecting the pits with readout light.

As an example of such pit-forming media,
A recording layer consisting of a light-absorbing dye is formed on a "substrate" and the dye is melted to form P/), or a recording layer containing a self-oxidizing resin such as nitrocellulose and a light-absorbing dye. Some are known to form pits by decomposing nitrocellulose, etc., and others are to coat a recording layer made of thermoplastic resin and light-absorbing dye and form pits by melting the resin and dye. It is being

However, in storage of such media, the dye may migrate and become mixed into the substrate, reagglomerate, recrystallize, or bleed out, resulting in decreased writing sensitivity and readout S/N. There is an inconvenience that the ratio may decrease. In particular, storage at high temperatures after recording
The pits are deformed and the read S/N ratio is greatly reduced.

Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to improve storage stability, and in particular to reduce deterioration of the S/N ratio due to high temperature storage after recording. The objective is to provide optical recording media.

Such objects are achieved by the invention described below.

That is, the present invention provides an optical recording medium having a recording layer made of a light absorber or a composition thereof on a substrate, in which two or more molecules of at least one type of dye are composed of -COO- groups or
Alternatively, it is an optical recording medium characterized by using a dye polymer connected by a divalent or higher linking group containing two or more -C00- groups.

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

The recording layer in the present invention is composed of a light absorber, and the light absorber is a dye polymer formed by linking two or more molecules of one or more kinds of dyes with a predetermined linking group.

The linking group in the present invention is -COO- group or -00
It is a divalent or higher group containing two or more 0- groups.

In the case of the latter divalent or trivalent or higher linking group, 2 to 3
COO or OCO is located at the above bond end.

As such a group, those of the following formula are preferable.

Formula (X)(L)n where L is O
represents CO or COO, n is an integer of 2 or more; group, or an imino group, or a combination of these, if necessary, bonded via a group such as -0-2-3- or -Co-).

In this case, n is preferably 2 to 6.

Note that two or more L's are usually the same, but may be different from each other.

Furthermore, a plurality of one or more types of linking groups represented by the above formula may be bonded to each other.

With such a linking group, two or more molecules of the dye (for example, two to
(approximately 1,000 molecules) are linked together to form a dye polymer.

In order to link dyes with such a linking group, it is preferable to follow the following procedure.

This makes synthesis extremely easy.

Furthermore, since there are no side reactions and the purity is high, there is no need for purification and the stability is high.

First of all, when using -Coo- group as a linking group, R
A total of two or more COO- groups and R'0CO- groups (usually,
Using one type of dye having 1 to 4 molecules each), the RCOO- group and the R'0CO- group are transesterified between molecules of the same type, and RCOOR' is eliminated. The dyes are linked with -COO-.

In such a case, R and R' in "-" are respectively,
Represents a substituted or unsubstituted alkyl group or aryl group.

In this case, R is a lower alkyl group, especially one having 1 carbon atom.
-2 unsubstituted or fluorine-substituted alkyl groups are preferred.

Further, R' is a lower alkyl group, especially a carbon atom number of 1 to
4 is preferably an unsubstituted alkyl group or an alkyl group substituted with fluorine or the like.

When R and R' are such lower alkyl groups, the resulting ester becomes volatile and the reaction becomes easy.

Alternatively, 2 of a dye having 1 or 2 or more (usually 2 to 4) RCOO- groups and/or R′0Co- groups
RCOO between different molecules using species-(usually two species)
- group and R′0CO- group are transesterified, RCO
By removing OR', different molecules (in some cases, between different molecules and between the same molecules) are linked through a -COO- group. In this case, synthesis becomes easier than in the above case.

In addition, using one or more types of dyes having one or more R'0CO- groups (R' is the same as above) and/or HO- groups, between the same and/or different molecules, Perform transesterification of R'0Co- group and HO- group,
R'OH may be removed and the same and/or different molecules may be linked via a -COO- group.

Furthermore, RCOO- group, R"0CO- group and HO-
Using one or more types of dyes having one or more of at least one type of groups, RCOO- group and R'0
It is also possible to link the same or different types of dyes by carrying out transesterification between the CO- group and between the R'OC〇- group and the HO- group.

Next, secondly, add two or more -Co〇- groups as described above.
When using a linking group with a valence of more than 2, the above RCO
One or more (usually one) dye having one or more of O- group, R'CO- group, and HO- group is added to one of the predetermined linking components. Transesterification of an RCOO- group and an R'0CO- group and/or an R''0CO- group and a HO- group is carried out between the species or two or more species.

In this case, the linking components are combinations that cause transesterification depending on the groups of the dye, such as RCOO- group, R”0
It has two or more of one or more of CO- groups and HO- groups.

That is, the connected component is (X)-t, corresponding to the above formula.
It has the structure l'Y-)n.

In this case, X is the same as above and Y- is RCOO-
group, R'OC〇- group or Ho- group, and n is the same as above.

Two or more Y's may be the same or different depending on the case.

However, if the Y's are different from each other, the reaction becomes complicated, so usually 2 to 6 Y's are the same, and this one type of connected component,
It is preferable to use one type of dye having 1 to 4 of one type of RCOO- group, R'0CO- group and HO- group in a combination that allows transesterification to occur.

In addition, "or" refers to unsubstituted or halogen-substituted chain (particularly preferably branched) hydrocarbons, alicyclic hydrocarbons, aryl groups (particularly benzene rings), heterocycles, imino groups, etc. A hexavalent residue or a combination of two or more of these, and furthermore, a combination of two or more of these and -〇-9-
Those in which S-, -CO-, etc. are bonded are preferred.

Moreover, in such a second aspect, (X)(' L)n
In addition to the linking group and repeats of (X)(L)n, a -COO- group may also be present as a linking group.

There is no particular restriction on the type of dye to be used, and 1. It is sufficient if it has a group of

The following dyes are particularly suitable as the dyes to be used.

Dl cyanine dye 2-thiazolyl, 2-(4,5-benzothiazolyl),
2-(naphtho(1,2-d)thiazolyl), 2-(naphtho(3,4-d)thiazolyl), 2-(phenanthrino(9,1O-d)thiazolyl), ?-benzoxasilyl, 2- Selenazolyl, 2-quinolyl, 4-quinolyl,
It has heterocyclic residues such as 2-benzimidazolyl at both ends, and these are substituted or unsubstituted 1,3,5°7-nonachitraenylidene, 1,3,5-heptatrienylidene, 3
．． 5-dimethylene-1,3,5-hebutatrienylidene, 2,4-neopentylene-1.3.5-hebutatrienylidene, 2-methine-4-propenyl L5.6-benzopyrylium, l, Linked with 3-pentadienylidene, 2-butenylidene, 3,5-2 trimethylene-1,3,5-hebutatrienylidene, etc.

In addition, because one of the heterocyclic residues has ten charges,
Substituents on the heterocyclic residue may have a single charge, or I, Br.

CuO4, BF4, P-) luenesulfonyl, p-
A salt may be formed with an anion such as chlorobenzenesulfonyl.

In these cases, the above group is bonded directly to the heterocyclic residue, more preferably to the N atom of the heterocyclic residue via an alkyl group or the like.

For example, 3.3'-di(6-hydroxyhexyl)-11-diphenylamino-10,12-ethylene-5,6,5',
6'-dibenzothiatricarbocyanine verchlorate, 3,3'-di(2-hydroxyethyl)-diphenylamino-10,12-ethylene-5,6,5',
6'-dibenzothiatricarpocyanine verchlorate, 3.3'-di(4-methoxycarbonylbutyl)-11
-diphenylamino-10,12-ethylene-5,6,
5',6'-dibenzothiatricarbocyanine verchlorate, 3.3'-di(2-acetoxyethyl)-11-diphenylamino-10,12-ethylene-5,6,5',6
"-dibenzothiatricarbocyanine verchlorate, 3.3'-di(6-acetoxyhexyl)-10,12
-trimethylene-pentatrienylidene-5,6,5'
, 6'-dibenzothiatricarbocyanine verchlorate, 3.3'-di(2-methoxycarbonylethyl)
-10,12-)rimethylene-pentatrienylidene-
5,6,5',6'-dibenzothiatricarbocyanine verchlorate, 1.1'-di(2-hydroxyethyl)-2,2'-1
Licarpocyanine verchlorate, l,1'-di(4-hydroxybutyl)-2,4'-tricarbocyanine verchlorate, 1,1'-di(4-acetoxybutyl)-4,4'-)
Ricarpocyanin barchlorate etc.

D2 Phthalocyanine dye The above group is directly attached to the benzene ring of the phthalocyanine dye,
More preferably a suitable linking group, such as -0CO-, -
COO-, -(ONH-, -9o 2-.

-502NH- etc. via an alkyl group bonded, etc.,
what is combined.

As the central metal atom of phthalocyanine, in particular, Pb,
VO, Mn, Sn, Cu, etc. are preferred.

For example, 3.3'-di(6-hydroxyhexyloxycarbonyl)vanadyl phthalocyanine, 5 3.3'-di(6-medoxycarbonylhexyloxycarbonyl)vanadyl phthalocyanine, 3.3'-di(6- acetoxyhexyloxycarbonyl) vanadyl phthalocyanine, etc.

D3 squarylium pigment - What is shown by. Here, A and B each represent an aromatic ring, and the following are particularly preferred.

Ba1
In the case of bar 1, R1 and R2 represent a substituent such as an alkyl group.

Particularly suitable are those in which the above group Y is bonded to an alkyl group.

For example, bis(2-hydroxy-4-dimethylaminophenyl)
Squalirium, 4-di(hydroxyethyl)aminophenyl-4'-diethylaminenaphthylsqualium, bis(2-acetoxy-4-dimethylaminophenyl)
squalirium, bis(4-(2-dimethoxycarbonylethyl)aminophenyl) squalirium, etc.

D4 Choline or Corol A compound in which the above group is bonded to choline or corol proposed in Japanese Patent Application No. 57-80487.

D5 Anthraquinone type, to which the above groups are bonded directly or via an alkyl group.

For example, 1,5-di(δ-hydroxybutylamino)anthraquinone, di(4-methyl-2-methoxycarbonylphenylamino)anthraquinone, di(4-methyl-2-acetoxyphenylamino)anthraquinone, and the like.

D6 Azo type, particularly bisazo type, trisazo type, azochrome type, etc., to which the above functional groups are bonded.

For example, methyl azobenzoate, azoacetylphenol, azo-2-hydroxynaphthalene-1'-hydroxybenzene, etc.

These dyes can be easily synthesized according to known methods.

9 On the other hand, the following are suitable as the connected component.

1) X(70H)n ethylene glycol, 1,3-propanediol,
1.4-butanediol, 1.5-bentanediol, 1,6-hexanediol, l,10-decanediol, 1.4-cyclohexanediol,
p,p'-dihydroxy-2,2-dicyclohexylpropane, bisphenol A1 hydroquinone,
p,p'-biphenol, hydroquinone dihydroxyethyl ether, polyethylene glycol (n=2
Dialcohols such as ~50), glycerin, sorbitol, etc., glucose, sucrose, etc., and their derivatives,
For example, ether.

2) X(-OCOR) n Lower (methyl, ethyl, etc.) ester of polyhydric alcohol of 1).

0 3)X+C0OR')n Terephthalic acid ester, trimellitic acid ester,
Polymellitic acid ester, dimethyl malonate,
Polyacid esters such as dimethyl succinate, dimethyl methylmalonate, dimethyl glutarate, ethylenediaminetetoacetate (including EDTA ester and partial ester), hydroxyethylenediaminetriacetate (HED)
TA ester), diethylenetriaminepentaacetate (DTPA ester), triethylenetetrahexaacetate (TTHA ester), etc.

4) X+0H) n i (OCOR) n 2 gluconate, partial ester of 1), etc.

5)X(-OCOR)n 2 (-COOR')n 3
Methyl bisacetyl dimethylol propionate, ethyl acetyl lactate, dinotyl acetyl malate, trimethyl acetyl citrate, dimethyl bis acetyl tartrate, etc.

6) X-(-COOR')n 3 (=OH)n 1 Methyl dimethylolpropionate, ethyl milk butyrate, dimethyl malate, trimethyl citrate, dimethyl tartrate, etc.

These connecting components are usually 0.1 to 1 mole of dye.
It is used in an amount of 2 moles, usually equimole, and is contained in the polymer in such a quantitative ratio.

Various methods can be used for transesterification in the formation of such dye polymers.

However, it is preferable to use an alkoxide of titanium, zirconium or aluminum as a catalyst from the viewpoint of ease of production, fewer side reactions, and ease of removing impurities.

Among these, the following are particularly suitable.

B1 Titanium alkoxide tetra-1-propoxytitanium (TPT), tetra-n
-Butoxytitanium (TBT), tetrakis(2-ethylhexoxy)titanium, tetrastearoxytitanium, TPT polymer (n = 2 to 10), TBT polymer (n-2 to 10), tributoxystearoyl titanium polymer (n = 2 to 1
0), di-propoxy-bis(acetylacetonato) titanate, di-n-butoxy-bis(triethanolaminate)
Titanate, dihydroxy-bis(raftate) titanate, (ethylene glycolate) titanium bis(dioctyl phosphate), titanium-1-proboxyoctylene gelicolate, 3-di-propoxy-bis(ethyl acetoacetate) titanate, tri-n- butoxytitanium monostearate, i-propoxytitanium dimethacrylate-i-stearate, i-propoxytitanium tris(4-aminobenzoate), i-propoxytitanium tris(dioctyl phosphate), and the like.

B2 Zircon alkoxide tetraethoxyzirconate, tetra-1-propoxyzirconate, tetra-n-propoxyzirconate, tetra-n-butoxyzirconate, tetra-t-butoxyzirconate, tetra-(2-methyl)butoxyzirconate , tetra-(3-methyl)benxyzirconate, 4-tetra-n-hebutyloxyzirconate, tetra-n-octyloxyzirconate, and the like.

B3 Aluminum alkoxide aluminum isopropylate, mono-5ee-butoxyaluminum diisopropylate, aluminum 5ec-butyrate, aluminum di-n-butoxide-mono-ethylacetoacetate, aluminum di-1-propoxide-mono-ethylacetoacetate, etc.

These catalysts may be used in an amount of about 0.1 to 10 wt% based on the dye.

Transesterification using such a catalyst is carried out in a single or mixed solvent such as dichloroethane, toluene, methyl ethyl ketone, methyl isobutyl ketone, etc.
The reaction may be carried out at a temperature of about 0° C., preferably under reduced pressure, while removing the produced lower ester.

Then, if necessary, the dye polymer may be separated and purified.

Although the recording layer of the medium of the present invention is made of such a dye polymer, the recording layer may also contain other resins separately.

At this time, the coating properties and coating properties are improved, and the recording sensitivity, readout S/N ratio, etc. are improved.

The resin used is preferably a self-oxidizing, depolymerizable or thermoplastic resin.

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

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

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

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

1ii) Vinyl chloride copolymer, for example, vinyl acetate-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, acrylic ester or methacrylic ester and vinyl chloride copolymers, acrylonitrile-vinyl chloride copolymers, vinyl chloride ether copolymers, ethylene or propylene-vinyl chloride copolymers, ethylene-vinyl acetate copolymers grafted with vinyl chloride, etc.

In this case, the copolymerization ratio can be arbitrary.

iv) Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

V) Polystyrene vi) Styrene copolymer 8 For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMA resin) , styrene-acrylic ester-acrylamide copolymer, styrene-butadiene copolymer (S
BR), styrene-vinylidene chloride copolymer, styrene-methyl methacrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

vii) Styrenic polymers such as α-methylstyrene, p-methylstyrene, 2
, 5-diglorstyrene, α, β-vinylnaphthalene,
α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as a copolymer of α-methylstyrene and methacrylic acid ester.

viii) Coumarone-indene resin Coumarone-indene-styrene copolymer.

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

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

In the formula, RIn represents a hydrogen atom or an alkyl group, and R represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R10 is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group.

Further, R20 may be a substituted or unsubstituted alkyl group, but the number of carbon atoms in the alkyl group is preferably 1 to 4, and when R20 is a substituted alkyl group, the alkyl group is substituted. The substituent is preferably a hydroxyl group, a halogen atom, or an amine group (particularly a dialkylamino group).

The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one of the atomic groups represented by the above formula An acrylic resin is formed by forming a homopolymer or copolymer in which the species or two or more species are repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer, for example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer 1, acrylonitrile-vinylidene chloride copolymer, Acrylonitrile-vinylpyridine copolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

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

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

The copolymerization ratio may be arbitrary.

xvi) Polyvinyl ethers such as polyvinyl methyl ether, polyvinylethyl ether, polyvinyl butyl 2 ether, etc.

xvii) Polyamide In this case, the polyamide includes nylon 6, Dillon 66, nylon 61o, nylon 612, nylon 9,
Nylon 11. In addition to ordinary homonylons such as nylon 12 and nylon 13, polymers such as nylon 6/66/610, nylon 6766/12, and nylon 6766/11, or modified nylons may be used in some cases.

! viii) Polyesters For example, various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipic acid, sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, and ethylene glycol. Condensates and co-condensates with glycols such as , tetramethylene glycol and hexamethylene glycol are suitable. Among these, condensates of aliphatic dibasic acids and glycols and co-condensates of glycols and aliphatic dibasic acids are particularly
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.

xix) Polyvinyl acetal resin Both polyvinyl formal and polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol are preferably used.

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

xi) Polyurethane resin Thermoplastic polyurethane resin with urethane bonds.

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

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

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

xiii) polycarbonates such as polydioxydiphenylmethane carbonate,
Polydioxydiphenylpro5 Various polycarbonates such as pancarbonate.

xxiv) Ionomer Na such as methacrylic acid and acrylic acid.

Li, Zn, Mg salts, etc.

xxv) Ketone resins, for example, condensates of cyclic ketones such as cyclohexanone and acetophenone and formaldehyde.

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

xxvii) Petroleum resins C5 type, C9 type, C5-cq, copolymer type, dicyclopentadiene type, or copolymers or modified products thereof.

xxviiiLJ-Blends of two or more of items i) to xxvii), or blends with other thermoplastic resins.

6 The self-oxidizing or thermoplastic resin may have various molecular weights.

Such self-oxidizing or thermoplastic resin and the above-mentioned dye polymer are usually deposited in a wide range of weight ratio of 1:0.1 to 100.

8 It is preferable that such a recording layer further contains a quencher.

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

Various quenchers can be used, but especially when the dye is excited and singlet oxygen is generated, -
It is preferably a singlet oxygen quencher that undergoes electron transfer or energy transfer from doublet oxygen to become excited, returns to the ground state M1 by itself, and converts - doublet oxygen to a triplet state.

A variety of singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with dye-binding resins. It is preferable. In this case, the central metal is preferably Ni, Co, Cu, Mn, etc., and the following compounds are particularly preferred.

1) Acetylacetonate chelate system 9 Qi N1 (II) Acetylacetonate Q2 C
u(II) acetylacetonate Q3 Mn(m) acetylacetonate Q4CO(II) acetylacetonate 2) Bisdithio-α-diketone system where R(11R(4) is a substituted or unsubstituted alkyl group or aryl group, and M represents a divalent transition metal atom.

In this case, M has a single charge and may form a salt with a quaternary ammonium ion or the like.

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl O N”(C:4H9)4 3) Bisphenyldithiol system (5) (8) Here, R and R are an alkyl group such as a methyl group, or It represents a halogen atom such as CI, and M represents a divalent transition metal atom such as Ni.

Furthermore, a and b are each 0 or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with a cation, and further, another ligand may be bonded below the - of M.

Examples of this include the following:

QIOPA-1001 (product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (product name manufactured by Mitsui Toatsu Fine Co., Ltd.)
Toluenedithiol)tetra(t-butyl)ammonium] Q12 PA-1003 (same as above) Q13 PA-1005 (same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 PA-1006 (same as above Ni- Bis(trichlorobenzenedithiol) tetra(t-butyl)ammonium] Q15 Co-bis(benzea-1,2-dithiol)tetrabutylammonium Q16 Co-bis(O-xylene-4,5-dithiol)tetra(t-butyl ) Ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis(O-xylene-4,5-dithiol)tetrabutylammonium3 LambQ19 Ni-bis(5-chlorobenzene-1,2-
Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol) Tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol) Tetrabutylammonium 4) Dithiocarbamine butychelate system (7) (8) Here, R and R represent an alkyl group. Moreover, M represents a divalent transition metal atom.

4 Q22 Ni-bis(dibutyl dithiocarbamic acid) [Antigen NBC (manufactured by Sumitomo Chemical Co., Ltd.]) 5) Bisphenylthiol type Q23 Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate type where M is a divalent transition Represents a metal atom. Also, M
has a single charge and may form a salt with a cation,
The benzene ring may have a substituent.

Q24 Ni-bis(thiocatechol)tetrabutylammonium salt 5 7) Salicylaldehyde oxime system (9) (1'O) Here, R and R represent an alkyl group, and M represents a divalent transition metal atom. .

Q25 Ni (II) O-(N-isopropylformimidoyl)phenol Q26 Ni (II)O-(N-dodecylformimidoyl)phenol Q27 Co (II)O-(N-dodecylformimidoyl)phenol Q28 Cu (II) O-(N-dodecylformimidoyl)phenol Q29 Ni (II) 2,2''-(trilomethylidine on ethylene bis)]-diphenol Q30 Co(II)2.2''-Cx trilomethylidine on ethylene bis)] -Diphenol Q31 Nt (H)2.2”-(1,8-naphthylenebis trilomethylidine)]-Diphenol Q32 Ni (II)-(N-phenylformimidoyl)phenol Q33 Co (II)-(N- Phenylformimidoyl) Phenol Q 34 Cu (II) (N 7 x
Nylformimidoyl) phenol Q35 N1(IT) salicylaldehyde phenylhydrazone Q36 Nt(II) salicylaldehyde oxime 8) Thiobisferrate chelate system (11) where M is the same as above, R and R (12 ) represents an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q37 N1(II) n-butylamino [2゜2'-
Thiobis(4-tert-octyl)-ferulate)
(Cyasorb-UV-1084 (American Cyanamid Co., Ltd.))Q3
8 Co(II) n-butylamino[2゜7 2'-thiobis(4-tert-octyl)-ferulate] Q39 Ni(II) -2,2'thiobis(4
-tert-octyl)-ferulate 9) Phosphonous acid chelate system (13) Here, M is the same as in 1■I, R and R (14
) represents a substituent such as an alkyl group or a hydroxyl group.

cI 8 40 In addition to this, other quenchers include the following.

10) Benzoate Q51 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Gaiki)] 11) Hindered amine Q52 Existing chemical substance 5-3732 (5ANOLL
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such an entcher is synthesized according to a known method.

These quenchers are generally used in an amount of 0.05 to 12 mol, particularly 0.05 to 12 mol, particularly 0.
．． It is contained in an amount of about 1 to 1.2 moles.

The maximum absorption wavelength of the quencher is preferably the same as the maximum absorption wavelength of the dye used.

As a result, reproduction deterioration becomes extremely small.

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

In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method.

The thickness of the recording layer is usually about 0.03 to 10 lumens.

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

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

Examples of solvents 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. , aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, and alcohol systems.

The material of the substrate on which such a recording layer is provided is not particularly limited, and may be any of various resins, glass, ceramics, metals, etc.

In addition, the shape varies depending on the purpose of use, such as tape, disk,
It may be a drum, a belt, etc.

Note that the base body usually has a groove for tracking.
Further, if necessary, it may have a base layer such as a reflective layer, a heat storage layer, a light absorption layer, etc.

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.

These substrates can also be coated with a primer to improve solvent resistance, wettability, surface tension, thermal conductivity, and the like.

As the brimer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, and the like can be used.

In addition, on the recording layer, if necessary, a reflective layer that functions as a back surface when using a transparent substrate, various uppermost protective layers, etc.
It is also possible to provide a single layer of half-mirror.

The uninvented medium may have the above recording layer 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, which is then 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 is irradiated with recording light in pulses while running or rotating. At this time, the dye polymer in the recording layer melts due to the heat generated by the dye polymer, 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 may be performed from the base side or from the recording layer side.

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

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

5. Specific Effects of the Invention According to the present invention, even if the medium is stored for a long period of time, there is very little deterioration in writing sensitivity or S/N ratio. In particular, the deterioration of the S/N ratio when read after recording and storage at a high temperature is extremely small.

Furthermore, the read S/N ratio is extremely high.

■Specific embodiments of the invention Specific examples of the present invention are shown below.

Example 1 As shown in Table 1 below, the following dyes and linking components were used in the molar ratios shown in Table 1, and transesterified with the following catalyst to obtain a dye polymer.

In this case, the catalyst amount was 1%, the solvent was dichloroethane, and the reaction was carried out at a reaction temperature of 40'O for 2 hours.

Then, the solvent was distilled off to separate the dye polymer.

As a result of thin-layer chromatography and liquid chromatography measurements, it was confirmed that 5 of these particles formed a dye polymer.

Next, these dye polymers or dyes were dissolved in dichloroethane and applied to a polymethyl methacrylate substrate which had been undercoated with titanium chelate at a thickness of 0.07 gm.

The dyes, linking components, and catalysts used are as follows.

Dye DI 3.3'-di(4-methoxycarbonylbutyl)-11-diphenylamino-10°12-ethylene-
5,6,5'',6'-dibenzothiatricarbocyanine verchlorate D2 3.3'-di(2-acetoxyethyl)-11-
Diphenylamino-10,12-ethylene-5,6,5
',6'-Dibenzothiatricarbocyanine Berchlorate D3 1,1'-di(4-acetoxybutyl) 4.4'
-) Licarbocyanin verchlorate, D4 1,1'-di(4-hydroxybutyl) 4.4
'-) Licarpocyanin Verchlorate D5 3,3'-di(6-medoxycarponylhexyloxycarbonyl)vanadyl phthalocyanine D6 3,3'-di(-acetoxyhexyloxycarbonyl) vanadyl phthalocyanine linking component Jl Malonic acid Dimethyl J2 Ethylene glycol diacetate J3 Methyldiethylenetriamine Pentaacetate J4 Methyl promellitic acid catalyst C1 Tetra-n-butoxy titanium C2 Di-propoxy bis(acetylacetonato) titanate C3 Tetra-n-butoxy zirconate C4 Aluminum tri-5ec- Butyrate For each sample prepared in this way, a semiconductor laser (830 nm) was focused on Igmφ while rotating at 1800 rpm, the power of the focusing part was 10 mW), and the pulse was 111100 n5.
I wrote it using ec.

After this, 1 mW semiconductor laser readout light was applied for 1 μs.
ec rll, 3 KHz pulse, and the reflected light was detected to measure the C/N ratio.

Each sample was then incubated at 50°C and 90% relative humidity.
After storage for 000 hours, the deterioration of the C/N ratio was measured.

Table 1 shows the deterioration rate (%) of the C/N ratio after storage.

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

Example 2 Sample No. 12.42 was obtained in which 30% by weight of resin was added to the dye polymer in samples No. 1 and 4 of Example 1.

The resin used was coumaron-indene resin (number average molecular 5
1,800), and poly-α-methylstyrene (number average molecular weight 80,000).

These results are shown in Table 2.

Table 2 Positive, 12 42 Resin CI Poly α-methylstyrene deterioration rate (z) 78 From the results shown in Table 2, the effects of the present invention are clear.

Example 3 Sample No. 13 was obtained by adding Quencher Q14 in an amount of 40% by weight to the dye in the dye polymer in Sample No. 1 of Example 1.

Table 3 shows the deterioration rate (%) of the reflectance when the sample cavity No. 1 was irradiated with readout light of 1 mW, Igs, 3 KH2 for 4 minutes.

Table 3 In addition, 113 Quencher Q14 C/N ratio deterioration rate High temperature storage deterioration C%) 7 5 Reflectance deterioration rate Reproduction deterioration (X) 35 3 From the results shown in Table 3, the present invention when containing quencher The effect is obvious.

Applicant TDC Co., Ltd. Agent Patent Attorney Akira Ishii - Continued from page 1 @ Inventor Akihiko Kuroiwa 3 TDC Co., Ltd., 13-1 Nihonbashi-chome, Chuo-ku, Tokyo Commissioner of the Patent Office Kazu Wakasugi Husband 2. Name of the invention optical recording medium 3. Relationship with the case of the person making the amendment Patent applicant's office
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) Representative of TDC Co., Ltd.
Kan Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
The statement in column 'f3, Detailed Description of the Invention j, of the supplementary description of contents on the 1st floor of Goyabe Building, Telephone: 988-16806, is amended as follows.

■) Third? Page 1? In the row, FNi, Co, Cu.

Mnj, f N i , Co , Cu ,
M n .

Correct as Pd and PtJl.

j 1) Acetylacetonate chelate QIN
i(II) Acetylacetonate Q2Cu(11) Acetylacetonate q3Mn(III) Acetylacetonate Q4Go(II) Acetylacetonate 2) Hisdithio-α-diketone system Here, R(11R(4) is substituted or unsubstituted Represents a substituted alkyl group or aryl group, M is Ni, Co,
Represents a transition metal atom such as Cu, Pd, or Pt.

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

Q5Ni(II) dithiobenzyl Q6Ni(IT) dithiobiacetyl 7 9 N”(C4H9) 4 3) Bisphenyldithiol system (5) (6) Here, R and R are an alkyl group such as a methyl group, or Cl represents a halogen atom such as M
is Ni, Co.

Represents a transition metal atom such as Cu, Pd, PL, etc. Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with a cation, and further, other ligands may be bonded above and below M.

Examples of this include the following:

QIO PA-1001 (Product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002c Same as above Ni-bis(toluenedithiol)tetra(butyl)ammonium] Q12 PA-1003 (Same as above)
Q13 FA-1005 (Same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 PA-1006 C Same as above Ni-bis(trichlorobenzenedithiol) tetra(L-butyl)ammonium] Q15 Co-bis( benzene/-1.2-dithiol)tetrabutylammonium Q16 Co-bis(0-xyL/7-4.5-dithiol)tetra(t-butyl) ammonium Q17N+-bis(benzene-1.2-dithiol)tetrabutyl Ammonium Q18 NI-bis(0-xylea-4,5-dithiol)tetrabutylammonium QI9Ni-bis(5-chlorobenzene-1,2-dithiol)tetrabutylammonium Q2ONi-bis(3,4,5,6-tetramethyl benzene-1,2 dithiol) tetrabutylammonium Q21Ni-bis(3,4,5,6-tetrachlorobenzene-1,2 dithiol) tetrabutylammonium 4) dithiocarbamate chelate system (7) (8) where R and R represents an argyl group. Moreover, M is Ni, Co, or Cu.

Represents a transition metal atom such as Pd or Pt.

Q22N+-bis(dibutyl dithiocarbamic acid) [
Antigen NBC (Sumitomo Chemical Company 5!) 5) Bisphenylthiol-based Q23Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate-based where M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as Pt. Further, M has a single charge and may form a salt with a cation, and the benzene ring may have a substituent.

Q24Ni-bis(thiocatechol)tetrabutylammonium salt 7) Salicylaldehyde oxime system (9) (10) Here, R and R represent an alkyl group, and 1M is Ni, Co, Cu
.

Represents a transition metal atom such as Pd or Pt.

Q25 Ni(II)o-(N-isopropylformimidoyl)phenol Q26 Ni(II)o-(N-dodecylformimidoyl)phenol Q27 Co(II)o-(N-dodecylformimidoyl)phenol Q28 Cu (II) o -(N-dodecylformimidoyl)phenol Q29 Ni (II)2.2'-(trilomethylidine on ethylene bis)]-diphenol Q30 Co(II)2.2'-(-r-ethylene bis Trilomethylidine)]-diphenol Q31 N1(II)2.2"-(1,8-naphthylenebis trilomethylidine)]-diphenol Q32 N1(II)-(N-phenylformimidoyl)phenol Q33 Co (II) - (N-), -=-rformimidoyl)phenol Q34 Cu(II) (N-), =rformimidoyl)phenol Q35 N1(II) salicylaldehyde phenylhydrazone Q36 N1(II) salicylaldehyde oxime 8) Thiobisferrate chelate system R(11)R(
12) Here, M is the same as above, and R(11), (12) and R represent an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q37 Ni (II) n-butylamino [2゜2
'-Thiobis(4-tert-octyl]-felt) (Cyasorb-UV-1084 (American Cyanamid Co., Ltd.)) Q3
8 Co (TI) n-butylamino[2゜2'-thiobis(4-tert-octyl)-fer-1.] Q39 N i (II) -2,2'-thiobis(4-tert-octyl)- Ferlate 9) Phosphonous acid chelate system Here, M is the same as above, and R(13), (14) and R represent a substituent such as an alkyl group or a hydroxyl group.

2 1 In addition to this, other quenchers include the following.

10) Benzoate Q41 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Gaiki Co., Ltd.) +1) Hindered amine Q42 1J chemical substance 5-3732 (5ANOLt
, 5-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]

Claims (1)

[Claims] 1. In an optical recording medium having a recording layer made of a light absorber or a composition thereof on a substrate, two or more molecules of at least one type of dye are combined with -COO- as the light absorber. What is claimed is: 1. An optical recording medium characterized in that it uses a dye polymer consisting of a group or linked by a divalent or higher linking group containing two or more -〇〇- groups. 2. The optical recording medium according to claim 1, wherein the atom or atomic group on the bond side of the linking group is 0 and/or CO. 3. The connecting group is -COO- group, RCOO- group, R
'0CO- group (herein, R and R' each represent one or two dyes containing at least one of alkyl (or aryl group) and HO- group) Between the species or more, the RCOO- group and R'0
3. The optical recording medium according to claim 1, wherein the dye is linked by transesterifying a CO- group and/or an R'0CO- group with a HO- group. 4. As a linking group, it has a divalent or higher group containing two or more -COO-, 3i, RCOO- group, R'oco-1 (
Here, R and R' each represent an alkyl group or an aryl group) and one or more types of dyes having one or two or more of at least one type of HO- group, and an RCOO- group, RCOO- Claim 1, wherein the dye is linked by transesterification between the group and the R'0CO- group and/or the R'0CO- group and the HO- group.
The optical recording medium according to item 1 or 2. 5. The optical recording medium according to any one of claims 1 to 4, wherein the transesterification is carried out using an alkoxide of titanium, zirconium, or aluminum as a catalyst. 6. Claim 1 in which the recording layer is made of a light absorber
The optical recording medium according to any one of items 1 to 5. 7. The optical recording medium according to any one of claims 1 to 5, wherein the recording layer is made of a composition of a light absorber, and the composition contains a resin. 8. Claims 1, 2, 3, 4, 5, and 7, wherein the recording layer is made of a light absorber composition, and the composition contains a quencher. An optical recording medium according to any of the above.