JPS59232894A - Photo-recording medium - Google Patents

Abstract

PURPOSE:To improve durability and prevent deterioration of S/N after high-temperature storage after recording, by forming a recording layer with a coloring matter-resin components connected with a special connecting group. CONSTITUTION:A recording layer is composed of coloring matter-resin component connecting more than two molecules of coloring-matter of one or more than two kinds to a resin through the specified connecting group. The connecting group represents one of higher than 2 valences including one -COO- group or more than two -COO- groups. In case of the latter provided with connecting groups of 2 valences or more than 3 valences, COO or OCO is located on the two or more than three connecting ends. The photo-recording layer of this kind features insignificant deterioration of filling-in sensitivity and S/N even for a long period of storage. Especially, deterioration of the S/N of reading-out after a high-temperature storage after recording becomes exceedingly insignificant. Further, the S/N of the reading out is extremely high.

Description

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

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because there is no contact between the medium and the writing or reading head.For this reason, many studies have been carried out on optical recording media. There is.

Among such optical recording media, heat mode optical recording media have the best light opening 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, and as an example, a part of the medium is melted and removed using a laser-like recording light, which is called a bit. The information Yυ is recorded in this bit, and this bit is detected at the read source and read.

Then, as one area of the medium for molding such bits, a recording layer made of a light-absorbing dye is placed on the substrate.
Forming bits by melting the dye 4. A recording layer containing a self-oxidizing resin such as luster, nitrocellulose, and a light-absorbing dye is provided, and a recording layer containing a self-oxidizing resin such as nitrocellulose and a light-absorbing dye is formed, and a recording layer containing a material that forms bits by fluorolysis such as nitrocellulose, or heat There are known methods in which a recording layer consisting of a plastic resin and a light-absorbing dye is coated, and bits are formed by melting the lubricant and the dye.

However, in such a medium, due to storage, the dye migrates into the C1 substrate, recondenses, and
Ii) Crystallization and brevi-out occur, resulting in disadvantages such as decreased writing sensitivity and decreased read S/N ratio.

Due to storage at high temperatures after VC and recording, the bits are deformed and the S/N ratio of the a-protrusion is greatly reduced.

I. Purpose of the Invention The present invention was made in view of the above-mentioned actual situation, and its main purpose is to improve the storage stability and, in particular, to reduce the deterioration of the S/N ratio due to high-temperature storage after recording. Record 'Mg:
Body Murasaki 1iA I'I'I'm going to do it.

Such object is constituted by the invention as described below.

That is, the first invention is.

At least one dye and 1Ω1 fat are composed of -COO- group, or -. The present invention is an optical recording medium characterized in that it has a recording layer on a substrate made of a dye-resin component which is connected and immersed in a divalent or higher connecting group containing two or more - groups.

Also, the second invention.

A dye-resin component formed by linking a dye of at least 1 fm to a resin with a divalent or higher linking group consisting of 1000- groups or containing two or more -000- groups, and a quencher. An optical recording medium characterized in that it has on a recording layer tg body consisting of.

■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 dye-resin component in which two or more molecules of one or more types of dye are linked to a resin via a predetermined linking group.

The linking group in the present invention is a divalent or higher group containing two or more %-000- groups or 1000- groups.

In the case of the latter divalent or trivalent or higher linking group, 2 to 3
000 or 000 is located at the above bond end.

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

Formula (X +-+L-) n Here, L! d,000 also represents ViCOO.

nl"l: Must be an integer greater than or equal to 2.

X is a divalent to trivalent or higher valent residue (especially a substituted or unsubstituted chain or cyclic hydrocarbon residue).

Heterocyclic residues, imino groups, and even this.

Combine these and make 10-, -8-, -00- as necessary.
bonded through a special group).

In this case, '#Kn is preferably 2-6, particularly 2-3.

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

Furthermore, one type or two or more of the linking groups represented by the above formula may be combined in an elaborate manner.

With such a linking group, a polymolecule of one type of dye is linked to the resin to form a dye-resin component.

K, which connects the dye and resin with such a linking group, is
It is preferable to follow the following. This makes the synthesis extremely easy, and there are no side reactions, the purity is high, and purification is not necessary.

Improved stability.

First, the first case is the case where -COO- group is used as a linking group, and aaoo- group and/or 7'ct;i: R10
Using a dye (usually one type) having 1 to 4 00-i (usually any one of them), R'0OO- crystal and /-! or coo- group (usually either of these), R,000- group and R'
Transesterification with the 000- group is performed to eliminate ⇠Ooo⇠', thereby linking the resin and the dye with -coo-.

In such a case, R and R' above each represent a substituted or unsubstituted alkyl group or aryl group.

In this case, 几 is a lower alkyl group, WK, carbon number 1
-2 unsubstituted or halogen-substituted alkyl groups are preferred.

Further, R' is a lower alkyl group, especially a carbon atom number of 1
-4 unsubstituted or halogen-substituted alkyl groups are preferred.

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

Or Vi, 几'000- group and/or HO- group (
Usually one or more (usually one to four)
one type or 21 or more (usually one type) of pigments having
A resin having an HO- group and/or a HO- group (usually either one) is used.

Perform transesterification of R' OOO- group and HO-7,J.

The resin and the dye may be linked through a -COO- group by removing R'OH.

Nao, ROOO- group, 1. Using one type or two or more types of dyes having at least one type of L'000-if, QoJ: and HO- group,
between the o- group and the R' OOO- group, and between the R' (JOO
carrying out transesterification between -, l and 1-10- groups,
It is also possible to link the dye and the resin.

Next, if necessary, as described above, it can be a divalent or higher linking group having two or more -COO- groups, and in this case, 1/'i, the above R000- group, R'000
- group and HO- group (usually one type)
or two or more (usually one or two or more (usually one) of 1 to 4 blue pigments, and +tao.

- group, R'000- group, and HO- group (usually one type) and one or more types of predetermined linking components (usually one type). CO〇- group and ⇠'oao- group, and/or ⇠'oco- group and HO
-carry out transesterification with the group.

In this case, the linking component is a group in which transesterification occurs depending on the group of the dye and the resin, that is, the linking component corresponds to the above formula.

(It has a structure of 1-(-Y)n.

In this case, X is the same as above, Y- is 几000- group, 几'oco-, 1 or I (e in O-AV), D, and n are the same as above.

And even if two or more Yjs are the same.

May be different.

However, if there are a large number of Y's, one reaction becomes complicated, so usually, 2 to 3111III's Y's are different, and this linking component, ROOO- group, 几' 000- group and I
1 type of dye carrying 1 to 4 of 1 type of O- group;

ROOO- group, 几'oco- group and H
It is preferable to use one of the O-methods and if1 fat in combination so that transesterification occurs.

In addition, as %X (well, chain hydrocarbon substituted with halogen etc., alicyclic ashing scale).

7 l) Divalent to trivalent residues such as -ru rings (%), hetero rings, imino groups, etc., or combinations of two or more of these, and in general, combinations of two or more of these and 10 -, -8
-, -00-, etc. are combined and 7hi is preferable.

Moreover, in such a second aspect, (X+−+L−)n
In addition to the linking group and the combination of (X←→L -) n, a -'ooo- group may also be present as a linking group.

Further, one dye may be linked to the resin +1jll chain via a linking group, or a number of dyes may be linked to the resin chain via a linking group.

There are no particular limitations on the type of dye used, as long as it has the above group.

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-[nando(3,4-d)thiazolyl), 2-Cphenanthrino(9,1O-d)thiazolyl], 2-benzoxasilyl.

2-selenazolyl, 2-quinolyl, 4-quinolyl, 2-
These have one telovalent residue at both ends, such as benzimidazolyl.

1,3,5゜7-nonachitraenylidene, 1,3,5-hebutatrienylidene, 3I5-dimethylene-1,3.5-hetutatrienylidene, respectively, , 2.4-unobentilene-1,3,5-hebutatrienyritene, 2-methine-4-propenyl-5,6
-Benzobyrylium 1, 3-'ntadienyritene,
2-butenylidene, 3.5-trimethyl l/ /1 +
Linked with 3 + 5-heptatrienylidene, etc.

In addition, by having one of the heterozygous residues +ta: tar, -f:■hetero J7 company residue [Okimata group may have a monomer, or I, Br.

(3t04.Bl4!+1-) Luenesulfonyl, p
-Chlorobenzenesulfonyl S The anionic salt may be formed.

In these two cases, the above-mentioned ink 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'-dibenzothiatricalzg'y 7-ni-no-rilolate.

3.3'-di(2-hydroxyethyl)-11-diphenylamino-10,12-ethylene-5,6,5',6
'-dibenzothiatricarbocyanine A-chlorate.

3.3'-di(4-methoxysulfonylbutyl)-11
-diphenylamino-io, 12-ethylene-5,
6,5',6'-dibenzothiatricarbocyanine chlorate.

3.3'-di(2-acetoxyethylhexyl)-11
--,7phenylamino-10,12-ethylene-5
,6+5'e6'-dibenzothiatricarbocyanine
Nomi-chlorate.

3.37-di(6-acetoxyhexyl)-10,3,
2-trimethylene-pentatrienylidene-5,6,5
', 6'-dibenzothiatricarbocyanine
Chlorate.

3.3'-di(2-methoxycarbonylethyl)-10
,12-trimethylene-pentatrienylidene-5+6
a5'16'-dibenzothiatricarbocyanine nomi-chlorate.

1.1/-di(2-hydroxyethyl)-:12'-1
1J cardocyanin barchlorate.

1.1'-di(4-hydroxybutyl)=214'-)
IJ calphocyanin verchlorate, 1,1'-di(4-acetoxybutyl)-4゜4'-
Tricarbocyanin, chlorate, etc.

D2 Phthalocyanine dye The above group is directly attached to the benzene ring of the phthalocyanine dye,
More preferably a suitable linking group, for example -000
-, -000-, -0ONI-1-, -8o2-.

-8o2NH- etc. via an alkyl group bonded to, etc.,
Bonded 5 As the central metal atom of phthalocyanine.

In particular, pb # vO, Mnt Sn l Ou, etc. are preferred.

For example, Vf.

3.3'-)(6-Hydroxyhexyloxycarbonyl)vanadyl phthalocyanine.

3.3'-,')(6-medoxycarbonylhexyloxycarzenyl)/nadylphthalocyanine.

3+3'-di(6-acetoxyhexyloxycarbonyl)hatidyl 7-talocyanine, etc.

D3 squarylium pigment - What is shown by. Here, A, B are respectively,
R2, which is an aromatic ring and preferably has a lower structure, is a substituent such as an alkyl group, and in particular, the alkyl group is preferably -OH, -C
Those to which functional groups such as oon and -003H are bonded are suitable.

for example.

Bis(2-hydroxy-4-1 methylaminophenyl)
Squalirium.

4-di(hydroxyethyl)aminophenyl-4'・-
Diethylaminonaphthyl squarylium, bis(2-acetoxy-4--)methylaminophenyl) squarylium.

Bis(4-(2-dimethoxycarbonylethyl)aminophenyl) squalirium, etc.

D4 Choline or Choline proposed in Collor Patent Application No. 80487/1987
Corole with the above groups bonded to it.

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.

D67zo series, especially bisazo series, trisazo series, azochrome series, etc.? and the above functional groups are bonded together.

for example, Methyl azobenzoate.

Azoacetylphenol.

Azo-2-hydroxynaphthalene-1'-hydroxybenzenato.

These dyes can be easily synthesized according to known methods.

The resin used is not particularly limited as long as it has a plurality of one or more of the above groups.

Those that can be particularly preferably used are listed below.

1) lI〇-group-containing resin nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose.

Cellulose esters such as ethylhydroxyethylcellulose or their derivatives, polyvinyl alcohol.

Polyvinyl acetate.

polyvinyl butyral, Polyvinyl formal.

Epoxy resin, Phenolic resin.

alkyd resin.

Polytyrosine.

Polyvinylhydroquinone.

Polyvinylbenzylhydroquinone.

methylolated polyacrylamide, Polyacrylic hydroxyamide.

Polyvinylmethylol.

Poly-(p-hydroxyethyl)styrene or copolymers thereof, and partial hydrolysates of esters such as ethylene-vinyl acetate copolymers.

2) R'0OO- group-containing resins Homopolymers of acrylic esters, methacrylic monoesters, etc. or copolymers with other monomers, or partial hydrolysates thereof, maleic anhydride, pyromellitic anhydride, anhydride Esterified products of copolymers of trimellitic acid and other monomers such as ethyl acetate.

3) IL 000-containing resin cellulose acetate, acetyl butyl cellulose polyvinyl acetate, formalized products or butyralized products of partial hydrolysates of polyvinyl acetate, etc.

(The number of the above-mentioned groups in snake fat is <b> 0.05 to 4 degrees per barb unit.

In addition, there is no limit to the molecular weight etc. of Samurai.

Such a resin is used in an amount of about 5 to 5 Qwt based on the amount of pigment decacephalic fat.

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

1)X-+0H)n ethylene glycol, 1,3-propanediol, 1,
4-butanediol, 1,5-bentanediol, 1,
6-hexanediol, 1.10-decanediol, 1
．． 4-Cyclohexanediol b p+ p'-dihydroxy-2e' 2- dicyclohexylzolonoξone, bisphenol A, nohydroquinone, p, p'-biphenol, hydroquinone dihydroxyethyl ether, IFIJ ethylene glycol (n=2-50 ) and other dialcohols.

Glycerin, sorbitol, etc.

Glucose, sucrose, its d conductor,
For example, ether.

2) Lower (methyl, ethyl, etc.) ester of polyhydric alcohol of X −+ OOO 几)nl).

3) X-+000FL')n Terephthalic acid ester, trimellitic acid di, X f /
l/, polymellitic acid ester, dimethyl malonate, dimethyl succinate, dimethyl methylmalonate, dimethyl glutarate, ethylenediaminetetraacetic acid ester (
EDTA ester (including partial esters), hydroxyethylenediamine triacetate (HE D
Polyhydric acid esters such as TA ester), diethylene triamine pentaacetic acid ester (DTPA ester), 1) polyethylenetetramine hexanoate ester (T T HA ester).

4) x-(oh■)nl-4-oao几). 2 gluconate ester, partial ester of 1), etc.

5) XAOOOO 几) n 2 + OOOFL')
methyl n3bisacetyldimethylolzolopionate,
Ethyl acetyl lactate, dimethyl acetyl malate, trimethyl acetyl citrate.

Bisacetyl (such as dimethyl tetratrate).

6) X-+0OOR')ns-+OII ln+methyl dimethylolpropionate, ethyl lactate, dimethyl malate, trimethyl citrate, dimethyl tartrate, etc.

These connecting components are usually 0.1 to 2 per mole of dye.
Molar, usually equimolar is used, and the color tone is determined by such a quantitative ratio.
It is included in the fat content.

Various methods can be used for transesterification to form such pigments and fat components.

However, it is preferable to use a titanium, zirconium or aluminum alkoxide 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 (TP'r), Tetocy n-butoxytitadi ('1''BT), Tetrakis (2-
ethylhexoxy) titanium, tetrastearoya cytidine.

T P'l'' polymer (n = 2-10), T
'B T polymer (n: 2~JO) %l-ributoxystearoyl titanium polymer (n-2~10).

Jimmy propoxy bis(acetylacetola-
t) Chitane.

DiI+-butoxybis(triethanolaminate) titanate.

Dihydroxy-bis(raftate) titanate.

(Ethylene glycolate) titanium bis(dioctylnoosphere-1.).

Titanium-i-probogysioctylene glycolate, seamy fluoroxybis(ethyl acetoacetate) titanate, tri-n-cytodried titanium monostearate.

1-proboxytitanomethacryl-1.-1-stearate.

i-Propoxytitanium tris(4-aminobenzoate).

-Zoroboxytitanium tris (dioctyl phosphate), etc.

B2 Zircon alkoxide Tetraethoxyzirconate.

-j tolar 1-f roboxysilconate.

Tetra-n-propoxyzirconate.

Tetra-n-butoxyzirconate.

Tetra-1-butoxyzirconate.

Tetra-(2-methyl)butoxyzirconate.

Tetra-(3-methyl)benxyzirconate
.

Tetra-n-hezotyloxyzirconate.

Tetra-ro-octyloxyzirconate, etc.

B3 Aluminum alkoxide Aluminum impropylate.

monocrown-butoxyaluminoinpropylate, Aluminum % - Butyrate.

Aluminum dirobe toxide mono-ethyl acetoacetate.

Aluminum di-1-propoxide-mono-ethyl acetoacetate and the like.

These catalysts range from 0.1 to 5 for 11 dyes and linking components.
It is sufficient to use about wt%.

Transesterification using such catalysts includes dichloroethane, toluene, methyl ethyl ketone.

The reaction is carried out in a single or mixed solvent such as methyl isobutyl ketone at a temperature usually from room temperature to about 80'C.
At this time, it is preferable to carry out the reaction under reduced pressure while removing the produced lower ester. Then, depending on the essence, the dye-resin component may be purified by a minute or a minute.

The recording layer of the medium of the present invention is composed of such a dye-resin component.

Other resins may be included separately.

Resins that can be suitably used are thermoplastic, self-oxidizing or depolymerizing resins, such as those described in Japanese Patent Application No. 58-1522.
There are some items listed in No. 9, etc.

It is preferable that such a recording layer further contains a quencher, which reduces the S/N by repeated irradiation with readout light.
The reproduction deterioration of the ratio is reduced and the light resistance is improved.

Various quenchers can be used as the quencher, but when the dye is excited and a term acid is generated at -I', the quencher undergoes electron transfer or energy transfer from -I' to excitation. state, and returns to the basal state by itself, and
- A singlet acid diquencher that converts doublet oxygen into a triplet state.

Various singlet oxygen quenchers can be used as singlet oxygen quenchers; Preferably, it is a compound.

In this case, 'd, Ni, Co as the central metal
, Ou, Mn, etc. are good.

In particular, the following compounds are suitable.

1) Acetylacetonate chelate QI N1 (1) Acetylacetonate Q2 0u (
If) Acetylacetonate Q3 Mn(III) Acetylacetonate Q4 0o(1) Acetylacetonate 2) Bisdithio-α-diketone system Here, R(1) to (4) are substituted or unsubstituted alkyl 5M represents a group or an aryl group 21111
] represents a transition metal atom.

In this case, 2M has a bulk charge and may form a salt with quaternary ammonium ions and the like.

Q5 N1 (11) dithiobenzyl Q6 N1 (II) dithiobiacetyl 7 9 Ni. (04)I9).

3) Hisphenyldithiol system, where fL (5) and R (6) L, l:, an alkyl group such as a methyl group, or Vi. M represents a halogen atom such as ot, and M represents a transition metal atom such as Ni. Furthermore, a and b are respectively 0-1:
The number is 4 or less.

Moreover, MI-1. of the above structure. - A salt may be formed with a cation with a weight, and further, other ligands may be bonded to the upper and lower sides of Mf7).

As such, there are the following.

Q 1 0 PA-1001 (Product name: Mitsui Toatsu Fine Co., Ltd.) Q 1 1 PA-1002 (N1-bis(toluenedithiol)tetra(t-butyl) ammonium as above) Q12 PA-1003 (same as above) Q 1 3 PA-1005 C Same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q 1 , i PA-1006 (Same as above Ni-bis(
Q150o-bis(benzene-1,2-dithiol)tetrabutylammonium Q160o-bis(0-xylene-4.5-dithiol)tetra(t-butyl)ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis(0-xylene-4,5-dithiol)tetrabutylammonium Q19 Ni-bis(5-chlorobenzene-1.

2-dithiol) tetrabutylammonium Q20 N+-bis(3,4,5,6-titramethylbenzene-], 2dithiol) tetrabutylammonium Q2], chlorobenzene-1,2-nothiol) te) butylammonium 4) dithiocarnocumic acid chelate system Herein, (7) and R<8)) represent an alkyl group. Also, Mii: coated with divalent transition metal atoms.

Q22Ni-bis(dibutyl dithiocarbamic acid) [
Antiquen NBO (manufactured by Sumitomo Chemical Co., Ltd.)] 5) Bisphenylthiol-based Q23 N-nihis (octylphenyl) sulfide 6) Thiocatechol chelate-based Here, Ml-1 represents a divalent transition metal atom.

Further, M has a -1a charge and may form a salt with a cation, and the benzene ring may be a substituted base stone.

Q24 Ni-bis(thiocatechol)tetrabutylammonium salt 7) Zarytylaldehyde oxime system Here, t(9) and 几゛l(j!) represent an alkyl group and represent a divalent transition atom of MVi.

Q25 N1(II)O-(N-isopropylformimimidoyl)phenol Q26 N1(II)o-(N-dodecylformimidoyl)phenol Q27 Co(II)0-(N-dodecylpo/L
/muimidoyl)phenol Q28 0u(1)0- (N-dodecylformimidoyl)phenol Q29 N; (l[)2.2'-(trilomethylidine on ethylene bis)]-diphenol Q30 Co(II)2 , 2'-C ethylene bis trilomethylidine)]-diphenol Q31 N1(L[)2 , 2'-(1,8-naphthylene bis trilomethylidine)]-diphenol Q32 N; (11)-(N-phenylform imidoyl)phenol Q33 Co(If)-(N-ferformimidoyl)phenol Q34 Ou(If)-(N-)x=nylformimidoylphenol Q35 N1(11) Salicylaldehyde phenylhydrazone Q36 N1(II ) salicylaldehye P oxime 8
) Thiobisferrate chelate system Here, Ml-j: Same as above, ,, (n) and θ group, lri, and alkyl group. It may also have an Mμ-charge and form a salt with a cation.

Q37 Ni(]1)n-butylamino(: 2,
2'-thiobis(4-tert-octyl)-fer-
'p) (Oyasorb-UV-1084 (Ameripnon Cyanamide Co, , Ltd,)) Q38
Co(■)n-butylamino(2,2'-thiobis(
4-tCrt-octyl)-phenolate] Q 39 N i (,If) -2+ 2'thiobis(4-tert-octyl)-phenolate 9) Phosphon, ゛H,2 chelate system where 1M is the same as above They are the same, and 几q■ and RO→ represent a substituent group such as an alkyl group or a hydroxyl group.

40 In addition to this, there are other quenchers such as the following.

10) Benzoate Q51 Existing chemical substance 3-3040 C Tinuvin-1
20 (manufactured by Ciba Geigy)] 11) Hindered amine Q52 Existing chemical substance 5-3 '/': U2L 5
ANOLLS-770 (manufactured by Sankyo Seikasha)] Such an encher is synthesized according to a known method.

And these quenchers are pre-i1i+2 dye-
It is generally about 0.05 to 12 moles, particularly about 0.1 to 1.2 moles, for every 1 mole of dye in 80% of the wall fat.

It is preferable that the maximum absorption wavelength of the quencher is greater than or equal to the maximum absorption wavelength of the dye used.

In this case, regeneration deterioration becomes extremely small.

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

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

The JLJ value of Kojiroku I is usually 0.03 to 1.
It has a stiffness of 0 μm.

In addition, such a recording layer may contain other dyes, other polymers or oryzamers, various plasticizers, surfactants, anti-banding agents, lubricants, flame retardants, stabilizers, dispersants, and crosslinking agents. -C may also be used.

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

Incidentally, examples of the vehicle used for coating include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and butyl acetate.

Ester systems such as ethyl acetate, carpitol acetate, butyl carpitol acetate, noether systems such as methyl cellosol, ethyl cellosol, or aromatic systems such as toluene and xylene.

tL 91 is good for dichloroethane 1 and halogenated alkyl-based and alcohol-based agents.

The material of the substrate on which such a recording layer is provided is not 11111 different, and each stone is high i;'=i)i
It may be made of glass, ceramics, or metal.

In addition, the shape of the tape depends on the intended use.

It may be a disk, drum, belt, etc.

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

In addition, the resin materials for the base include polymethyl methacrylate-1, acrylic tjt'm i epoxy white resin,
Polycarbonate (9J fat, polysulfone resin, polyether sulfone, methylpentene polymer, etc.), which does not have miso and does not have miso, is suitable.

It is also possible to coat these substrates with a primer on the surface to improve their properties, solvent resistance, wettability, and heat transferability. .

As the primer, grJ Zubo, titanium thread, silane-based, aluminum-based coupling agents, various photosensitive TJ resins, etc. can be used.

Ushida, Record 1 - Depending on the μ on the top, place the transparent substrate once on each spot (reflective J-, the uppermost layer of α-protective layer, /・- It is also possible to provide a mirror.

Since the medium of the present invention can have the above-mentioned recording information on one side of such a body, 4) it is possible to write the recording information on both sides of the body. (It is also possible.

Alternatively, use two recording layers coated with 1* 'a: coating 1; You can also protect it from dust and scratches.

(2) Specific Effects of the Invention The medium of the present invention is placed under a running V/) rotation and is irradiated with recording light in a pulsed manner. At this time, the dye-resin component is melted by the light heat of the dye in the dye-kl 1lit component in the recording layer, and a bit is formed.

The bits formed in this way are read out by detecting the reflected light or transmitted light from the readout source, or the reflected light, while the medium is running or rotating.

In this case, recording and reading are preferably performed from the base side, but may also be performed from the recording layer side.

It is also possible to erase the pin 7) once formed on the recording layer using photo-tanning heat and rewrite.

Note that the recording or reading light may be a semiconductor laser, a He-Ne laser, or an Ar laser.

A He-Od laser or the like can be used.

(2) 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.

According to the second invention, in addition to these, light resistance against playback deterioration and the like is significantly improved.

■ Specific implementation sequence of the invention Specific examples of the present invention are shown below.

Example 1 As shown in Table 1 below, with the following dyes.

The resin was used at the molar ratio and weight shown in Table 1, and was subjected to ester conversion using the following catalyst to obtain one dye-resin component.

In this case, the amount of catalyst is 1wt, and the amount of solvent is.

Dichloroethane was used for one reaction, and the reaction was carried out at ψ4o°C for 2 hours.

Next, the medium M was distilled off to separate the pigment and fat components.

As a result of thin layer chromatography and liquid chromatography (1-1), it was confirmed that the dye was linked to the tree.

Then these dyes - 1irj IJ & components or dyes.

On a polymethyl methacrylate substrate which had been bath dissolved in dichloroethane and undercoated with Ariiso titanate, 0.
The coating was applied to a thickness of 0.07 μm.

The dyes, resins, and catalysts used were as follows.

Dye DI3.3'-di(4-methoxycarbonylbutyl)-
11-diphenylamino-10,12-ethylene-5,6,5'.

6'-Dipenzothiatricylpocyanine chlorate D23,3'-di(2-acetoxyethyl)-11-.
Diphenylamino-10,12-ethylene-5+615
',6'~Dipenzothiatricarbocyanine nomi-chlorate D31.1'-di(4-acetoxybutyl)-4,4'
-Tricarbocyanine Nomi-chlorate D41,1'-di(4-hydroxybutyl)-4,4'
-1-Rical mouse cyanine Nono-chlorate D53,3'-di(6-medoxycarbonylhexyloxycarbonyl)/nadylphthalocyanine D63e3'-di(6-acetoxyhexyloxycarbonyl)vanadyl phthalocyanine resin R1 Polyvinyl butyral C number average molecular weight 100,000, 0I
- I25 section) R2 cellulose acetate C number average molecular weight 100,000, esterification rate 39.4%) 3 Ethylene-vinyl acetate copolymerization (number average molecular weight 8
10,000, copolymerization ratio 50%) 几4;j1' Limethyl methacrylate (number average molecular weight 100,000) Catalyst 01 TBT 02 1=-propoxy-bis(acetinate) For each sample prepared in this way, 1800
While rotating at rpm, a semiconductor laser (830 nm
) to converge the light to 1 μm, the output of the converging section is 10 m W ), and the ξ width is 100 nsec? It's one.

After this, the 1 mW semiconductor laser readout light is applied at 1/js.
cc rll, irradiated as a 3KHz nollus.

The reflected light was detected and the 07N ratio was measured.

Each sample was then incubated at 50°C and 90% relative humidity.
After storage for 000 hours, the deterioration of the 0/N ratio was measured.

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

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

Example 2 In Sample No. 1 of Example 1, 5 dyes - 40 inches of quencher Q1 in weight ratio to the dye in the resin component
Sample No. 12, in which 4 was added, was obtained.

Sample No. 1, 12, 1 mW, II
Table 2 shows the deterioration rate (h) of the CZN ratio when the readout light of Is, 3)G(z) was irradiated for 4 minutes.

Table 2 Sample quencher-Q14 0/N ratio deterioration rate High temperature storage deterioration (fed) 7 Reflectance deterioration rate Regeneration deterioration (%) 5'3 4 From the I paste shown in the second, the second invention The effect is obvious.

Applicant: TDC Co., Ltd. Representative Patent Attorney Yo Ishii - Procedural 7 Municipal Court - Written (self-motivated) June 2, 1982, 2, Name of invention Optical recording medium 3, Comparison with the case of the person making the amendment Related Patent Applicant Office
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) TDC Co., Ltd. Representative Hiroshi Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
Goyabe Building 1st Floor Telephone: 988-16806, The description in the section 5'F Detailed Description of the Invention in R30 of Details of Amendment 4g is amended as shown in C.

■) In the first line of page 91, fNi, Co, Cu.

Mnj means rNi, Co, Cu, Mn.

Correct as Pd, Pt, j.

II) The descriptions from line 3 on page 31 to line g on page 40 are corrected as follows.

fl) Acetylacetonate chelate QINi (I
I) Acetylacetonate Q2Cu(II) Acetylacetonate Q3 Mn(III) Acetylacetonate Q4Co(II) Acetylacetonate 2) Hisdithio-α-diketone system Here, R (11(4) is a substituted or non-1δ represents an alkyl group or an aryl group, and M is Ni, Co,
S represents a transfer 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(II) dithiobiacetyl N”(c4H8)4 3) Hisphenyldithiol system (5) (6) Here, R and R are an alkyl group such as a methyl group, or a zero sentence, etc. /\ represents a rogen atom, etc., and M is Ni, Co.

Represents a transition metal atom such as Cu, Pd, or Pt. 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:

QIOPA-1001 (product name Mitsui Toatsu Fine Co., Ltd.!M) Qll PA-1002 (times J-HNi-his(toluenedithiol)tetbutyl)ammonium] Q12 PA-1003C times '2) Q13
FA-1005 (same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 FA-1006C times Above Ni-bis(trichloropenzenedithiol) tetra(t-butyl)ammonium] Q15 Co-bis( benzene-1,2-dithiol)tetrabutylammonium Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl) ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni- Bis(0-xylene-4,5-dithiol)tetrabutylammonium Q19Ni-bis(5-chlorohensen-1,2-dithiol)tetrabutylammonium Q2ONi-bis(3,4,5,6-tetramethylbenzene-1, 2 dithiol) tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1,2 dithiol) tetrabutylammonium 4) dithiocarhemic acid chelate system (7) (8) where R and R represents an alkyl group. Moreover, M is Ni, Co, or Cu.

Represents a transition metal atom such as Pd or Pt.

Q22 Ni-bis(dibutyl dithiocarbamine M
) (Antiken NBC (manufactured by Sumima Kagaku Co., Ltd.)] 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 l! ! 7) Salicylaldehyde oxide system (9) (10) Here, R and R represent an alkyl group, and M 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-dotesylformimidoyl)phenol Q29 Ni(II)2.2' (trilomethylysine on ethylene bis)] -diphenol Q30 Co(II)2.2'-(: trilomethylysine on ethylene his) )]-diphenol Q31 Ni (H) 2.2'C
1,8-naphthylenehis to trilomeka lysine)]-diphenol Q32 Ni (II) -(N-phenylporumimidoyl)phenol Q33 Co (II) -(N-phenylporumimidoyl)phenol Q34 Cu (n ) =(N-7,=lupormimidoyl)phenol Q35 N1(II) salicylaldehyde phenylhydrazone Q36 N1(II) salicylaldehyde oxime 8) Thiobisferrate chelate system R(11) R(
12) (11) Here, M is the same as above, and R (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)-ferulate) (Cyasorb-UV-1084 (American Cyanamid Co., Ltd.)) Q3
8 Co (II) n-butylamino[2゜2'-thiohis(4-Lert-octyl)-ferulate] Q39 Ni (II) -2,2'-thiobis(
4-tert-octyl)-ferulate 9) Phosphonous acid chelate system (13) Here, M is the same as above, R (14) and R is a substituted group such as an alkyl group or a hydroxyl group, ( represents.

In addition to this, other quenchers include the following.

10) Benzate Q41 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Gaiki)] 11) Hindered amine Q42 Existing chemical substance 5-3732 C5ANOLL
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.) J

Claims (1)

[Claims] 1. At least one type of dye and a resin, -000
- group or linked by a divalent or higher linking group containing two or more -〇〇- groups - A light characterized by having a recording layer made of a resin component on the washing body. recoding media. 2. The atom on the bond side of the linking group - or the atomic group. The optical recording medium according to item 1 of the scope of patent 6jj, which is CO2 and CO2. 3 The linking group is -000- group, I(, cOO- group, IL'000-,!ig (where R and R
′ represents an alkyl or aryl group, respectively)
and 1r with at least 11 folds of HO- groups
One type of pigment having i2 or more, or two or more types of Vi, and R
between the resin having at least one of the OOO- group, the R'000- group and the HO- group; The optical recording medium according to claim 1 or 2, wherein the dye and the resin are linked by transesterification with a - group. 4. 2 containing two or more -COO- groups as a linking group
has a group having a valence or higher, and at least one of a ROOO- group, an R'OC〇- group (herein, R and R' each represent an alkyl group or an aryl group), and a HO- group.゛Also, one or more types of dyes having two or more +ri, and ⇠C00- group, ⇠'ooo- group and HO
- a resin having at least one kind of groups, and ROOO
- group, R'000 group, and H, O- group, or two or more of the connecting components, The optical recording medium according to claim 1 or 2, wherein one dye and the resin are linked by transesterification between the R'000- group and the HO- group. 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 At least one pigment and a resin, -000-
or a dye-resin component connected by a divalent or higher linking group containing two or more -000- groups;
An optical recording medium comprising a recording layer comprising a quencher on a substrate. 7. The optical recording medium according to claim 6, wherein the atom or atomic group between the bonds of the linking group is 0 and/or 00. 8 The linking group is -000- group, 几00〇-group, 几'
ooo- group (herein, R and R' each represent an alkyl group or an aryl group) and J-1-0-
One or more types of dyes having at least one group or 1 to 122 or more groups, and a ROOO- group, 几'0
at least one ffI to the 00- group and HO-
between the resin and the resin. Claim 6, wherein the dye and the resin are linked by transesterification between the TL OOO- group and a'ooo--H and/or the a'ooo--H and HO-J9. or the optical recording medium described in item 7. 9. As a linking group, it has a divalent or higher group containing two or more -COO- groups, and the ROOO- group and l'000-
(herein, % 几 and R' each represent an alkyl group or an aryl group) and one or more dyes having one or more of at least one of the group IJ, 0-, , 几CO〇- group, R'0OO- group and I-10- group, at least 11 of the aooo- group, R'0OO- group and HO- group are 2 between the ROOO- group and one or more connecting components having R'000
-Claim 6 or 7, wherein the dye and the resin are linked by transesterification between the -l and/or R'000- groups and the f(O- group). 10. The optical recording medium according to any one of claims 6 to 9, wherein the transesterification is carried out using an alkoxide of titanium, zirconium, or aluminum as a catalyst. 11. The optical recording medium according to any one of claims 6 to 10, wherein the quencher is a transition metal chelate compound.