JPS60203489A - Optical recording medium - Google Patents

Abstract

PURPOSE:To raise the signal to noise ratio of reading by preventing the decrease of the reflection factor of recording layer, by providing the substrate layer composed of the paint film of the colloidal particle dispersion liquid of silicon condensation product between the resin substrate and the recording layer composed of coloring matter (composition). CONSTITUTION:The colloidal particle dispersion liquid of silicon series condensation product of 30-100Angstrom in particle diameter is prepared by a method wherein silicon tetrachloride is hydrolyzed and condensated in ethyl alcohol and ethyl acetate or the line. Then, this colloidal particle dispersion liquid is coated on the acrylic resin or polycarbonate resin substrate transparent to write light and read light, dried and the substrate layer of 50-500Angstrom in thickness is formed. Then, the recording layer containing coloring matter (for example: cyanine coloring matter and phthalocyanine coloring matter) and if necessary, resin (for example: nitrocellulose) is formed by a thickness of 0.04-0.12mum level to be the aimed optical recording medium.

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 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 small holes are formed to perform writing, information is recorded using the pits, and the pits are detected with readout light and read out.

Until now, most of these pit-forming type media, especially those using a semiconductor laser as a light source that can make the device smaller, have a recording layer made of a material mainly composed of Te.

However, in recent years, because Te-based materials are harmful, and there is a need to increase sensitivity and reduce manufacturing costs, organic materials, mainly dyes, are being used instead of Te-based materials. There are an increasing number of proposals and reports on media using recording layers.

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

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

Techn'o1. , 1B (1) 105 (198
1) ) and metal phthalocyanine dyes (JP-A-57-8
No. 2094, No. 57-82085), etc.

There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Laid-Open No. 88795/1983).

In both of these, the recording layer FJ BQ is formed by vapor deposition of dye.
There is no major difference from Te-based media in terms of media production.

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 achieve a large S/N ratio.

In addition, if a transparent substrate carrying a recording layer is integrated with the recording layer facing each other, which is a so-called air sand inch structure, and writing and reading are performed through the substrate, the recording can be recorded 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 made of a dye-deposited film, 1. Usually, an anode is added between the substrate and the recording layer.
A vapor-deposited reflective film such as the following is interposed.

In this case, the vapor-deposited reflective film is intended to increase the reflectance and improve the S/N ratio, and the reflective film may be exposed due to pit formation and the reflectance may increase, or in some cases, the reflective film may be removed. It removes the reflectance and reduces the reflectance.
Naturally, recording and reproduction cannot be performed through the substrate.

Similarly, JP-A-55-teteso4 Niha, IR-1
32 dye (manufactured by Kodak) and polyvinyl acetate.
'-diethyl-2.2''-trivalent luposyanine iodide and nitrocellulose;
Y., Law, et al., Appl., Phys.

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 a vapor-deposited film of vanadyl phthalocyanine exhibits a slightly high reflectance (P, Kivitj, etal, Ap
pl, Phys, Palt A 28 (2) 1
01 (1981).

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, 1p-P-8 (1980)], and a proposal based on this was made in JP-A-58. -112790, these dyes have low solubility in solvents, are easily crystallized, and are extremely unstable against readout light, causing them to immediately decolorize, especially when applied as a coating film. , cannot be put to practical use.

In view of these circumstances, the present inventors first developed an indolenine-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. It has been proposed to use it as a single layer model (Japanese Patent Application Nos. 57-134397 and 57-134170).

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. (Patent Application No. 57-182589, Patent Application No. 57-177778, etc.)
.

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a transition metal compound quencher to cyanine dyes to prevent regeneration and deterioration.
(Japanese Patent Application No. 57-IH832, No. 57-188048, etc.)

Furthermore, they have proposed forming an ionic bond between a dye and a quencher, thereby further reducing regeneration deterioration and increasing stability (Japanese Patent Application Nos. 59-14848 and 59-18878). No. 59-19?15).

Incidentally, such a dye or dye composition is applied as a coating film as a recording layer on a resin substrate that is transparent to writing light and reading light, and writing and reading are performed particularly from the back side of the substrate. In such cases, the surface of the resin substrate may be damaged by the coating solvent during coating.
This has the disadvantage that the reflectance of the recording layer decreases and the S/N ratio for reading cannot be sufficiently high.

Furthermore, during long-term storage, there is a risk that dyes and other additives may dissolve and diffuse into the substrate resin, resulting in a decrease in reflectance.

Furthermore, writing causes damage to the substrate such as dents and stripes due to heat, which also lowers the S/N ratio. Moreover, the noise after erasing increases.

On the other hand, the present inventors used Ti, Zn as the base layer.
, proposes the use of a hydrolyzed coating film of KIRE-I compound such as A5L (Japanese Patent Application No. 57-232198, No. 5).
7-23219θ etc.).

Thereby, the above-mentioned disadvantages are improved.

However, the preparation conditions and coating conditions for the base layer coating solution are strict,
Furthermore, the coating solution lacks storage stability, making it difficult to obtain a consistent base layer, and since it has a refractive index, it has disadvantages such as a decrease in reflectance.

Furthermore, although silane solution hydrolyzate coatings and silicon oxide vapor deposited coatings are known, these are insufficient in terms of imparting solvent resistance and heat resistance to the substrate.

II. OBJECTS OF THE INVENTION An object of the present invention is to improve the underlayer interposed between the substrate and the recording layer in an optical recording medium having a recording layer made of a dye or a dye composition on a resin substrate. The purpose is to lower the refractive index and improve the S/N ratio.

These objects are achieved by the invention described below.

That is, the present invention has a base layer made of a coating film of a colloidal particle dispersion of a silicon-based condensate on a resin substrate, and a recording layer made of a pigment or a pigment composition on this base layer. This is an optical recording medium characterized by:

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

A dye is contained in the recording layer of the optical recording medium of the present invention.

There are no particular restrictions on the dyes to be used, including cyanine, phthalocyanine, and naphthalocyanine.

Tetradehydrocholine or tetradehydrocholor type, anthraquinone type, azo type, triphenylmethane type,
Any pigment such as biryllium or thiapyrylium chlorine can be used.

Under these circumstances, the main effect of the present invention is the first one.
It is a cyanine dye.

Among the cyanine dyes, those represented by the following formula (I) are preferred.

Formula (I) Φ-L='i' (X-) m In the above formula (1),! and Φ represents an indole ring, a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, a pyridine ring, etc. to which an aromatic ring such as a benzene ring, naphthalene ring, or phenanthrene ring may be fused.

These Φ and! may be the same or different, but
They are usually the same, and various substituents may be bonded to these rings.

In addition, Φ means that the nitrogen atom in the ring has ten charges, and! is one in which the nitrogen atom in the ring is neutral.

These Φ and! As the skeletal ring, the following formula [ΦI]
~ [Φ store] is preferable.

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

(R4)Q [Φ■] [+”] (R4)Q [Φ■) (R4) q (ΦX] (Ra) q 罷1 [Φ光] In these various eggs, the nitrogen atom in the ring ( In the imidazole ring, the group R* (R1
, R1') is a substituted or unsubstituted alkyl group or aryl group.

In such a ring, the group R,,R1' bonded to the nitrogen atom
There is no particular restriction on the number of carbon atoms in the group. When this group further has a substituent, examples of the substituent include a sulfonic acid group, an alkylcarbonyloxy group, an alkylamido group, an alkylsulfonamide group, It may be any of an alkoxycarbonyl group, an alkylamine group, an alkylcarbamoyl group, an alkylsulfamoyl group, a hydroxyl group, a carboxy group, a halogen atom, and the like.

In addition, when m described below is 0, the group R1 bonded to the nitrogen atom in Φ is a substituted alkyl or aryl group,
and - has an electric charge.

Furthermore, Φ and! When the ring is a fused or non-fused indole ring (formula [Φwork] to [ΦIT)], the third
At the position, two substituents R2.

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

On the other hand, Φ and! At a given position in the ring represented by
Furthermore, another substituent R4 may be bonded. Such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, aryloxy groups,
Alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamido group, alkylcarbamoyl group, arylcarbamoyl group, Alkylamine groups, arylamino groups, carboxylic acid groups, alkylsulfonyl groups, arylsulfonyl groups, alkylsulfonamide groups, arylsulfonamide groups, alkylsulfamoyl groups, arylsulfamoyl groups, cyano groups, nitro groups, etc. may be a substituent.

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

Among these, those having a fused or non-fused indole ring of the formulas [Φ] to [Φ■] are preferred.

These have excellent solubility in solvents, coating properties, and stability, exhibit extremely high reflectance, and have extremely high readout S/N ratios.

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

Formula (LI) CH=CH-CH=CH-C=CH-CH=CH-CH
Formula [Lm] CH-C=CH-CH ↓ Here, Y represents a hydrogen atom or a monovalent group. In this case, the monovalent group includes a lower alkyl group such as a methyl group, a lower alkyl group such as methoxynol, etc. alkoxy group, dimethylamino group, diphenylamino group, methylphenylamino group,
Di-substituted ami7 groups such as morpholino group, imidazolidine group, ethoxycarbonylpiperazine group, fulkylcarbonyloxy group such as acetoxy group, furkylthio A (such as methylthio group), cyano group, nitro group, halogen such as Br, C1, etc. Preferably, it is an atom.

Among these formulas (LI) to [L■], tricarbocyanine linking groups, particularly formulas [LII] and (Lm), are preferred.

Furthermore, X- is an anion, and preferable examples thereof include I-, Br-, CIO4-, BF4-+C
Examples include H30SO3-, C1-C>SO3-, and the like.

Note that m is 0 or l, but when m is 0, R1 of Φ usually has one charge and becomes an inner salt.

Next, specific examples of cyanine dyes of the present invention will be listed, but the present invention is not limited to these.

LL-LL'
) CH3CH3 D2 (ΦI) CH3CH3 D3 CΦI) C2H40HCH3 D4 (Φ I) (CH2) 3 503 2 CH
3' (CH2)3 S03 Na" D5 (ΦII) CH3CH3 D6 (Φm) (CH2) 3 303 2 CH3
' (CH2)3 SO3Na'' D7 (Φm) CH2CH20HCH3D8 (Φm
) (CH2)20COCH3CH3[+9 (Om]
(CH2)20COCH3CH3D10'(Φm)
CH3CH3 Dll (Φm) CH3CH,3 D12 (ΦI) ' C1s H37CH3013
(ΦI) C4H9CH3 D14 [ΦI) CHOCOCHs CH38! B D15 [ΦI] C7H14CH20HCH3TLL
”--Eee again -X- -(Lll) HI -(Lll) H0 sentence 04 - (Lm) HI Br -[LII) H- -(L II) HCI O4 -(Lll) H- -(Lll) H0 sentence 04 -(Lll) HBr -(LII[) -N(C6H5)2 1 0 sentence 04-
'(Lll) H0 sentence 04 - (LII+) -N (C8H5)2 1 0 sentence 0
4- (Lll) HI -CLII) ″ Hc intersection 04 - (Lm) -N (C8H5)2 1 0 sentence 04-
[LII) H Eu Sashi"Sie" Upper Beni-H D16 [ΦII) C8H17co3 -DI? (
Φtn) C8H17CH3-D18 [ΦIII)
CHC,OO-CH3(714 -C7H14COOH D19 [ΦI[I) C7H,4COOC2H5CH
3-D20 [ΦrII] C4H9CH3-D21
(Om) ClBH37CH3-D22 [Φm]
Ca Hs C) (3-D23 [ΦI) C17H3
4COOCH3CH3-D24 [ΦI) CHOC
OCH3CH3'8 1B D25 [ΦI] C8H17C2H5-D2B [Φ
Engineering) C7H15C2H5-D27 [ΦII) C
HCOOCH3CH3-734 D28 [ΦI■] C3H16CH20COCH3C
H3L -¥-Mata -Ei- (L II) HCMata04 (L II) H- (Lll) HBF4 (Lm) -N(C6H5)2 1 0 Sentence 04 (Lll
) H, C or 04 (L II) ) I C or 04 (L II) HI (Lm) -N (C8H5)2 1 1 (L II
)) I I (LII)', I (I (L II) HC sentence O4 fiJIt O'P R upper Yu ni'-F!j-Yu jLI
R4-D30 [ΦII] C7H14COOCH3C
21 (6-D31 [Φm,) C7H14CH201
(CH3-D32 [Φm) C, Hl, CH20CO
C2H5CH3, -D33 [Φr11), C,7H
34COOC2H5CH3-D34 [Φm] C17
H35CH3-D35 [Φm] C7I(,5, C2
H5-D36 [ΦIV) CH3CH3-D37
[ΦIV) CH3CH3-D38 [ΦIV) C4H9CH3-D38 [Φ■
) (CH2)2 0COCH3CH3-D40 (O
V) C2H5-4-CI (3D41 (OV) CH
3-4-CH5D42 [ΦVL)' C2R5--
D43 [ΦVl] C2H5-5-C intersection D44 [Φ
Vl) C2R5-5-OCRD45 [ΦVl) C
2R5-5, -0CR Earthwork Earthwork (L It ) H0 sentence 04 (L II ) H0 sentence 04 (L II ) H1 (Lm) -N (C8R5) 2 1 I (LIV)
HI I (L II ) HI (Lll) H, I (L II ) H0 sentence 04 [LI■] H0 sentence 04 (L II ) HI [LII) H■ (L II ) H1 , (Lll) HBr (Lm) -N(C6H5)2 1' Br3 (L
II) HCH3C:6H4So33 (Lll)
HBr ``j beg'' Beniyo anus' first L'' Yu TLL LD46 [Φ
Vl), C2H5--(Lrll)D47[ΦVl)
C2H5, --(Lll)D48[ΦVl) C2H5
--(L'I)D49[Φm) C2H5--'(Ll
l) p50 [Φ■] C2H3--[LV] p51 [φVl) C2H5--(LV) D52 [ΦV
l) C2H5--(LVI)D53 [Φ■] (CH
2) 30COCH3-[L■]D54[ΦVl] CH
2CH20H-5-Cl (Lll)D55 [Φ劃C
2H5-'-[Ll! ]-(LII3 D5B [Φ■] C2H5- D57 [ΦIX) C2H5-(Lm) D58 [Φ■]
C2H3--[L■]-(Lll) D, 59[ΦX) C2H5- = (LII3 080 [4)XI) CI(,C)1. OHY sentence
X -I Br HBr HBr cl(3Br HI Br HI Br -1Br -N(C6H5)2 1 C) I3C6H4So3HC
) 13C6H4S03 HBr HBr OCH31,I HI HBr Friendly Man 1EjlL工1上 Shu'yu Shi.

D131 (Φ■) C2H5-- D62 [Φ■] (CH2) 30COCH3--D6
3 [Φ torture] C2H5- D64 [Φ] CH2CH2CH2503H-D6
5 [Φ store] C2H3 D86 [ΦXll+), C2H5--D6? [Φ
Twin) C2) 15 - -- 4-Cl5 D8B [Φ■) C3H1□ D69 [Φ■) Cl8H37- D70 [ΦVl) C3H1□ ---5-〇Cross D71 (Φ■) C3H17 D72 [Φ■] Cl8 H37 -5-C sentence-0CH3 D73 (('vI) 0B HI3 '6-0CH3
D74 [Φ■3 C8H,? -5-0CH3D75
[Φ■) C8H17-5-C sentence L--Eichi -l-
x- (L II ) HI (Lrl) H1 (Lm) -N (Cs Is) 2 1 Cl04
(LIII) -N (Ca Hs) 2 1 I(
Ill) HBr (Lll) HBr (Lll) HI (Lm) -N(C8H5)2 1 Br(Lll)
HCl04 (Lm) -N (CB H5')2 1 C cross04 (
LII) HI (L II) HI (LIV) -1I CLm) N (C8H5) 2 1 Br■ Beg'Mo-1'Shini' Yu Red D76 [ΦVl) C, 8H37-5-C See D77
[ΦVl) C8H,7-- D78 [ΦVl) C8H,7-- D73 [ΦVT) C,8H375-Cl1)8Q
(ΦVl) Cl8H37-5-CgLD81 (Φ■
) C8H17--D82 [ΦVl) C3H1□ --D83 (ΦV
I) C3H17 D84 [Φ■) C3H1? -- D85 [Φ■) Cl8H37-- D86 [Φ■) Cl5H27-- D87 (Φ■) C13H2? --D88 [Φ■
) C8H17-- D88 [Φ■) C8H17-- D80 [Φ■) Cl8H37-- L Earth Earthwork (Lm) -N (C8H5) 2 1 B r (LI
I (Lll) HI (L II) HCH3G6H45O31 (L II
) HC;C61(,5O3(LV) HI I (LVI) HI Br [L■]-■ (Lllll)' -N (C6H5)2 l Br(L
II) HCH3C3H4S03(Lll) HB
r (LIE) HBr (Lm (, Lllll) 0CR31 Engineering (L II) H, CJI3C8H, So3 blood situation
Free boat 1L-1 upper' LL-fli 1 soil D91 [
Φ■) C8H17-- D82 [Φ■] Cl8H3゜ --D93 [Φ scale] C8H17-- D94 [Φ mowing) C8H, □ -- D85 [Φ mowing] C8H,. -- D86 [Φ mowing] C, 3H27-5-GKLD87
[Φ cut] C3H1□ -- D98 [Φ■) Cl8H3□ D89 [Φ store] C8H17 -- Dloo (Φ twin) C8H, □ --Dlol (O
V) C8H,7,--D102 (Φ■) C3H1
□ --0103 (Φ store) C3H1? -- D104 (ΦI) CHCHOCOCH3CH3-2 0105 (Φ■) CH2CH20HCH3-DlOB
[Φm) CH3CH3- 1--■- Sentence X (L II) HC) 1308) 14SO3 (Lm)
-NCC6H5)2 1 C)13C6H4SO3(
Llri HBr (Lll) 'HI (Lll) HI (Lm) N(C8H5), 2 1 Br(Lm) -
N(C8H5)2 1 Br(Lll)l(Br (L II ) HB r (Lll) HBr (Lll) HBr (Lll) HBr (L II ) H0 sentence 04 (Lll) HBr (LVI) B r I ClO4 Blood Meng Man 1E%P lLLl 工' lLLlE -&Sat DAO7 (ΦI) CH3CH3- p108 [Φm) CH3CH3- 0109 (ΦVl) C2H5-6-C! 10110
(ΦVl) C11HI7-6-C sentence DIll (
Φ)ffll) C2HEl --DI+2 , (ΦV
l) CH3CH3-01+3 (ΦVl) CH3C
H3-L Y Sentence
H-0 sentence 04 [L ■) HC intersection 04 (Lm) N (C6) 15) 2 0 C104 (Lll
) H-, C 04 Furthermore, the second phthalocyanine dye has the greatest effect according to the present invention.

There are no particular restrictions on the phthalocyanine used, and examples of the central atom include Cu, Fe, and Co.

N, In, Ga, Ai, InC3L, InBr.

InI, GaCl, GaBr, GaI.

AfCl, AMBr, Ti, TiO, Si.

Ge, H, R2, Pb, Vo, Mn, Sn, etc. are possible.

In addition, the benzene ring of phthalocyanine can be directly or via an appropriate linkage, -OH, halogen, -COO
H, NR2, -CoC1, -COOR', -0COR
' (However, R' is various alkyl or aryl, etc.)
, -5o2c sentence, -5O3H1-CONH2, -CN,N
Various substituents such as O2, -3CN, -3H1-CH2CM, etc. may be bonded.

Such dyes can be easily synthesized according to the method described in Nitrogen-Containing Heterocyclic Compounds I, page 432, Dai Organic Chemistry (Breakfast Shoten).

That is, first, the corresponding Φ'-CH3 (Φ' represents the ring corresponding to Φ) is heated with excess R and I (R1 is an alkyl group or an aryl group), and R1 in Φ' is is introduced into a nitrogen atom to obtain Φ-CH3I-.
Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde, hydroxyaldehyde, pentagonal or isophorone using an alkali catalyst such as piperidine or trialkylamine, or acetic anhydride.

Such a dye can also form a recording layer alone.

Alternatively, a recording layer is formed together with resin.

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

The self-oxidizing resin contained in layer #i undergoes oxidative decomposition when the temperature rises, and among these, nitrocellulose is particularly preferred.

Further, the thermo-iq plastic resin is softened by increasing the temperature of the dye that has absorbed the recording light, and various known thermoplastic resins can be used as the 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 copolymer For example, ethylene-vinyl acetate copolymer.

Ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 octapolymer, ethylene-maleic anhydride copolymer, ethylene propylene terpolymer (EPT)
)Such.

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

111) Vinyl chloride copolymer, for example, vinyl acetate-vinyl chloride copolymer, 11! Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, copolymer of acrylic acid ester or methacrylic acid ester and vinyl chloride, acrylonitrile-vinyl chloride copolymer, vinyl chloride ether copolymer, ethylene or propylene-vinyl chloride copolymer,
Such as those obtained by graft polymerizing vinyl chloride to ethylene-vinyl acetate copolymer.

In this case, the copolymerization ratio can be arbitrary.

1t) Vinylidene filtration copolymer Vinylidene chloride-vinyl chloride copolymer, hnylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

V) polystyrene i) styrene copolymer {for example, styrene-acrylonitrile copolymer (AS
resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-acrylic acid ester-acrylamide copolymer, styrene-butadiene copolymer (SBR), Styrene-11! vinylidene chloride copolymer,
Styrene-methyl methacrylate copolymer, etc. .

In this case, the copolymerization ratio can be arbitrary.

ii) Styrenic polymers such as α-methylstyrene, p-methylstyrene, 2
, 5-dichlorostyrene, α.

β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic acid ester.

viii) Coumarone-indene resin Coumarone-indene-styrene co-T (coalescence).

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

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

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

Further, R20 may be a substituted or non-monosubstituted alkyl group, but it is preferable that the alkyl group has 1 to 8 carbon atoms, and when R20 is a substituted alkyl group, The substituent substituting the alkyl group is preferably a hydroxyl group, a halogen atom, or an amino group (particularly dialkylamino, ti).

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 An acrylic resin is formed by forming a homopolymer or copolymer having one or more repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer such as acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-true 112 vinylitine copolymer, acrylonitrile-vinylpyridine copolymers, acrylonitrile-methyl methacrylate copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-butyl acrylate copolymers, etc.

In this case, the copolymerization ratio can be arbitrary.

・l Self) Dia-7ton Acrylamide Polymer Dia-7ton acrylamide polymer made by reacting acetone with acrylonitrile.

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 alcohol, etc.

xvii) Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-10, nylon 6-12. In addition to regular homonylons such as nylon 9, nylon ll, nylon 12, and nylon 13, nylon 6/6-6/6-1
0, nylon 6/6-6/l 2. Nylon 6/6-6
Polymers such as /11 or modified nylon may also be used.

xvii) polyesters with various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipic acid, cepasthenic acid, or aromatic dibasic acids such as isophthalic acid, terephthalic acid; Condensates and co-condensates with glycols such as ethylene glycol, tetramethylene glycol and hexamethylene glycol are suitable.

Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable. 'Furthermore, for example, a modified gliptal resin, which is a condensate of phthalic anhydride and glycerin, is esterified and modified with a fat, natural resin, etc., and the like may also be suitably used.

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

In this case, the degree of 7-cetalization of the polyvinyl acetal resin can be arbitrary.

xx) Polyurethane resin Thermoplastic polyurethane resin with urethane bonds.

Particularly suitable are polyurethane resins obtained by condensation of glycols and cyisocyanates, especially polyurethane resins obtained by condensation of alkylene glycols and alkylene diisocyanates.

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.

X 1ii) Polycarbonates such as polydioxydiphenylmethane carbonate,
Various polycarbonates such as dioxydiphenylpropane carbonate.

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

Li, Zn, Mg salts, etc.

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

+++1vi) 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.

xxviii) A blend of two or more of the above i) to xxvii), or a blend with other thermoplastic resins.

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

Such self-oxidizing compounds or thermoplastic resins and the above-mentioned dyes are usually combined with heavy! Ji-ratio: 1:0.1-
Layered with a wide E: ratio of 100.

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

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

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

Various quenchers can be used, but in particular, when the dye is excited and single-claw oxygen is produced,
- Shigenobu It undergoes electron transfer or energy transfer from oxygen and becomes an excited state, returns to the ground state by itself, and -m
Preferably, it is a singlet-resistant quencher that converts butyric to the triplet state.

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

l) Acetylacetonate chelate Ql-I Ni(II) acetylacetonatochelate Ql-
2 Cu(II) acetylacetonate Ql-3 Mn
(m) Acetylacetonate Ql-4 Co(II) Acetylacetonate 2) Bisdithio-α-diketone system 4 represented by the following formula: Here, R - R represents a substituted or unsubstituted alkyl group or aryl group. where M is Ni, Co, Cu,
Represents a transition metal atom such as Pd or Pt.

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

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

σ σ Ci σ σ 3) Hisphenyldithiol system represented by the following formula, where R5 to R8 are hydrogen or methyl, (,
Alkyl groups such as ethyl groups, haloken atoms such as C1,
Or 7 such as dimethylamino group, diethylamino group, etc.
Represents a mino group, M is Ni, Co, Cu, Pd, P
Represents a transition metal atom such as L.

Furthermore, M in the above structure has a single charge and may form 44 with a cation (Cat) such as a quaternary ammonium ion, and further above and below M.

Furthermore, other ligands may be bound.

Examples of this include the following:

σ C1d σ σ σ σ σ 0 σ010/ c
IO' (7σ σ σ σ
45027 t+ and those described in Japanese Patent Application No. 58-163080.

4) Dithiocarbamic acid chelate system represented by the following formula: where R9 and R10 represent an alkyl group; M represents a transition metal such as Ni, Co, Cu, Pd, or Pt;

5) What is shown by the following formula 1M is here! Represents a transfer metal atom, Ql is and Cat represents a cation.

M Rainbow Cat Q5-I Ni Q'2 2CHN◆(CH3)363
3 Q5-2 N i Ql2 2G(C4H8)4N+Q
5-3 Co Ql2 2C(C4H8)4N"Q 5
-4 Cu Q 12 2CCC4H8)4N"Q 5
-5 P d Q 12 2C(C2H9)4N+Others described in Japanese Patent Application No. 125654/1983.

6) Those represented by the following formula, where M represents a transition gold atom, and R11 and R12 are cN and coR”pc, respectively.
o OR'ICON R represents "?R16 or 5O2R", R13 to R17 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and Q2 represents a 5-membered or 6-M IEi Represents a necessary atomic group; Cat represents a cation; n is 1 or 2;

2'-Lightning 2 (%INヱ 88 2- 22202 - ~ cQ size ■ II　I　II　I Coco Co coo C0 σ　σ　CI　σ　07　σ In addition, those described in Japanese Patent Application No. 58-127074.

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

M Cat Q 7- I N i 2 ((II-C4H9)3N
:]Q7-2Ni2(n-T), 16H
33 (CH3-3N) In addition, patent application 1986-1 '2
What is written in 7075 inches.

8) Bisphenylthiol system Q 8- I Ni-bis(octylphenyl) sulfide 9) Thiocatechol chelate system represented by the following formula, where M is Ni, Co, Cu, Pd, Pl A-
represents a transition metal atom of f.

In addition, M has one charge, and cation (Cat) and liA
may be formed, and the benzene ring may have a substituent.

M Cat Q9-I Ni N” (C4H9)410) A compound represented by the following formula, where R18 represents a monovalent group or is θ~6, and M represents a mole gold hA atom. and Cat represents a cation.

M　R”　l　Cat QIO-I N i HON (n-C4H8).

Q 10-2 N i CH31N(n-C4H9)4
What is described in Japanese Patent Application No. 143531/1982.

11) Compounds represented by the following formulas: 20212223 in the formula ゛ above, where R, R, R and R each represent a hydrogen atom or a monovalent group, and R, R, R and R27 represents a hydrogen atom, 24 25 2B or a monovalent group, but R and R, R and R, and R28 and R27 24252526 may be bonded to each other to form a 6-membered ring.

Moreover, M represents a transition metal atom.

Σ１　；　； 匡１　工　I Ctl:G engineering Country 10: Engineering Country 1 engineering σ　σ In addition, those described in Japanese Patent Application No. 58-145294.

12) A compound represented by the following formula, where M represents Pt, Ni or Pd, and Xl
, X2, X3, and X4 each represent O or S.

L Nirage N1 Ni K soil Q12-I Ni OOO0 Q12-2 Ni S S S S In addition, those described in Japanese Patent Application No. 58-145295.

13) Compound represented by the following formula, where R31 is a substituted or unsubstituted alkyl group or aryl group, R, R, R and R35 represent a hydrogen atom 32 33 34 or a monovalent group, R32 and R33, 3334
3435 R and R, or R and R may be bonded to each other to form a 6-membered ring.

Moreover, M represents a transition metal atom.

14
) The compound represented by the following formula 41 41 43 R, R, R and R44 each represent a hydrogen atom or a monovalent group, or 41 42 4
2 43 43 44 R and R, R and R, and R and R may be bonded to 11 to form a 6-membered ring.

5 In addition, R and R46 are a hydrogen atom or a monovalent No1 (
represents.

Furthermore, M represents a transition metal atom.

, 41 R42R43R44R45! l! 48 MQ1
4-1) I H) I HH-old Q 14-:l' HHC4H70COHHNl In addition, those described in Japanese Patent Application No. 151929/1981 15) Compounds represented by the following formula, 51 Ha51 52 53 54 55 Here , R, R, R, R, R.

56 57 R, R, and R58 are each a hydrogen atom or 1
R51 and R52, R52 and R53, R53 and R54,5
55G' 58 57 R and R, R and R, and R57 and R58 may be bonded to tlH to form a 6-membered ring.

X represents halogen.

M represents a transition metal atom.

σ　σ In addition, those described in Japanese Patent Application No. 58-153392.

18) Salicylaltehydoxime system represented by the following formula, 610 where R and R61 represent an alkyl group, and M is Ni, Co, Cu, or Pd.

Represents a crystal transition metal atom such as Pt.

u 60 u 8-IM Q l 6-1 1-C3H71-C3H7N iQ
16-2 (CH) CH(CH2),,CH3N i
211 3 Q l 6-3 (CH) CH((182),,C)
I3C.

211 3 Q l 6-4 (CH) CH(CH12),,cH
3C.

211 3 Ql6-5 C6H5C6H5Nj Q16-8 C6H5Cs H6C.

Ql 6? C6H5C6H5Cu Q16-8 NHCsHh NHO2Hh N1Q16
-9 0HOHNi 17) Thiohisferrate chelate represented by the formula
1. System where M is the same as above, %5 and R66 are:
Represents an alkyl group. Further, 1M has a 1' charge and may form a cation (Cat) and a j-line.

566 RRM Ca-T Q 17-1 t-CHN i N"H3" (C:4H
8) 8 1? Q l 7-2 t-CHCON”H3 (C4H8)
17 Q17-3 t-C'HNi - 17 1B) Phosphonous acid chelate system represented by the following formula 2◇72 (R)d Here, M is the same as above, and u 7 + and R7
2 represents a substituent such as an alkyl group or a hydroxyl group.

172 1--yo RM Q 18-1 3-t-CH, 5-t-C4) 19.8
-0) I Ni9 tS) Compound 787 represented by each person below, where R, R, R and R84 are hydrogen 81 82
83 1j; (represents a child or a monovalent group, but 81 82 8
2 83 83 84 R and R, R and R, and R and R may be bonded together to form a 6-membered ring.

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

R86 represents a hydrogen atom, hydroxyl), (or a 16-substituted or non-[delta]-substituted alkyl group, or an aryl group).

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

Z represents a nonmetal b:(child group) necessary to form a 5- or 6-membered ring.

M represents a transition metal atom.

21　;　;　; , l l l l 1 t1ee: 77 =:: 16CI In addition, those described in Japanese Patent Application No. 58-153393.

20) Compound represented by the following formula, where R91 and R92 are each a hydrogen atom,
Substituted or unsubstituted alkyl group, aryl group, acyl group, N-furkylcarbamoyl group, N-arylcarbamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, alkoxycarbonyl group or aryloxycarbonyl group , M represents a transition metal atom.

R91u 92 M Q20-1 nC4Hg CH3N1 Q20-2 CN3 CH30-φ-N) IcONi In addition, those described in Japanese Patent Application No. 155359/1982.

In addition, other quenchers include the following.

l) Benzoate type Q 21-1 Existing chemical substance 3-3040 (Tinuvin-120 (manufactured by Ciba Geigy)) 2) Hindered amine type Q22-1 Existing chemical substance 5-3732 (SAN, 0
LLS-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Each of these quenchers has a concentration of 0.01 to 1 mole of dye.
It is contained in an amount of about 12 moles, particularly about 0.05 to 1.2 moles.

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

This makes regeneration and deterioration extremely small.

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

Note that in order to downsize the device, kf or 750.780.83 is required as a light source for writing and reading.
0nm semiconductor laser or 633nm He-N
Since it is preferable to use an E laser or the like, the maximum absorption wavelength of the heavy D1 oxygen quencher is 680 nm or more, particularly 680 to 1500 nm, and even more preferably 800 to 150 nm.
Preferably, it is 0 nm.

Furthermore, it is preferable that εD/εQ is 3 or more when the absorption coefficients of the dye used (when two or more types are used, their effective I+I+) and -modifier (oxygen quencher) are SD and εQ at the wavelength of the readout light. .

In addition, when using two or more kinds of dyes in combination, the absorption maximum wavelength and SD of the dyes are arithmetic mean effective values depending on the concentration.

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

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

As a quencher-dye ion conjugate, patent application No. 59-
Those described in No. 14848 may also be used.

However, what can be used more suitably is the patent application filed in 1973.
It is a conjugate of a cyanine dye cation and a quencher anion described in No. 9-18878 and No. 59-1!11715.

The cyanine dye cation used may be any of the cations listed above.

The quencher anion is 3) above.

It may be any anion form among 5), 6), 7), 9), 10), and 17).

A specific example is given below.

In addition, in the following, D+ is the corresponding cation of D, and Q- is the corresponding anion of quencher.

Dl q knee SDI D" I Q"'3-8 SD2 D" I Q-3-15 SD3D+IQ-3-15 SD4 D" 10 Q-3-3 SD5 D" 10 Q-3-15 SD6D"17Q73-8 SD, 7D+2IQ-3-8 SDB D 10 II Q"'3-8 SD9 D+8 Q-3-8 5010D" 8 Q-3-2 SDIID+9Q-3-15 S 012 D", 106 Q"' 3- 15SD1
3D+toQ-3-15 SDI4 0+ 5 Q-3-15 SDI5 D+ 10 Q-3-7 3D16 D" 22 Q-3-15 SD17 D" 105 Q-3-185018D"
7 Q-3-17 SDIII D” 20 Q-3-[1SD20 D+
I Q"'3-1 5 D21 D" I Q-3-2 SD22 D+ I Q-3-16 SD23 D "I Q-3-17 SD24 'D" 10 Q-3-7 SD25 D" 108 Q- 3-8 SD26 D” 108 Q-3-7 3D27 I)+ 108 Q-3-2SD28 D
"106 Q-3-18SD29 D" 5 Q-3
-8 SD30D+5Q-3-, 2 SD31D"5Q-3-7 SD32 D" 5 Q-3-18 SD34 D" I Q-3-8 SD35 D" I Q-3-3 SD36 D+ 10 Q"'3- 1 SD37D+17.Q-17-I Sn2OD" II Q-10-I SD39 D + 2I Q-7-2 SD40 D+ 9 Q-10-1 5D41 D" IQe Q-6-I SD42 D" 5 Q-3- 3 SD43 D ◆ 42 Q-3-8 SD44D"109.Q-3-8 SD45D+70Q-3-8 SD4'8 D+ 110 Q-3-8SD47 D+
70 Q-3-15 3D48 D+ 42 Q-3-17 SD411 D” 43 Q-3-7 SD50 D+ 91 Q-3-8 SD51 D+ 111 Q-3-8 SD52 D+ 112 Q-3-2 SD53 D+ 113 Q-3-8 SD54 D+ 70 Q-2-3 A quencher having such absorption characteristics is appropriately selected and used depending on the light source and dye used.

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

The thickness of the recording layer is usually about 0.03 to 2 μm. Alternatively, when forming a recording layer using only a dye and a quencher, vapor deposition, sputtering, etc. may be used.

The thickness of the recording layer is 0.04 to 0.121 Lm, particularly 0.04 to 0.121 Lm.
It is preferable that it is 05-0.081Lm.

At 0.04 Bm, especially below 0.031 Lm, the absorption amount and reflection (6) are both small and it is not possible to obtain large write sensitivity and rIj raw sensitivity.

If it is 0.12 μm or more, the pre-group will be buried, making it difficult to obtain a tracking signal. Also,
It is not easy to form bits, and writing sensitivity decreases.

In addition, such a recording layer may contain other dyes, other polymers or oligomers, various u (plastics, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, oxidants). An inhibitor, a crosslinking agent, etc. may also be included.

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

Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl isopnal 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, halogenated alkyl systems such as dichloroethane, alcohol systems, etc. may be used.

The substrate on which such a recording layer is provided is made of resin.

Various resin materials are available.

However, among such resins, acrylic resins are particularly susceptible to the various coating solvents mentioned above, especially ketones, esters, alkyl halides, etc., and the effect of the base layer of the present invention is particularly large. Or polycarbonate 4M resin.

Since these are substantially transparent to writing and reading light, writing and reading can be performed from the back side of the substrate, which is advantageous in terms of sensitivity, S/N ratio, etc., and is also effective against dust. It is also advantageous in terms of implementation.

Furthermore, since the moldability is good, it is easy to form tracking grooves.

Acrylic resins include polymethyl methacrylate, etc.
Preferably, a copolymer or homopolymer of a methacrylic acid ester having a chain or cyclic alkyl group having 1 to 8 carbon atoms is used.

Furthermore, as the polycarbonate-1 resin, bisphenol A type is preferred.

When these acrylic resins or polycarbonate resins are formed by injection molding,
The effect of the base layer of the present invention is even greater.

In addition, it is preferable that the number average degree of polymerization of these acrylic resins or polycarbonate resins is about 800 to 6,000.

Further, it is preferable to form a hole for tracking on the surface of the substrate on the recording layer side.

The base layer consists of four films of a colloidal particle dispersion of a silicon-based condensate.

Colloidal particles of silicon-based condensate include silicon halide,
Particularly suitable are silicon tetrachloride or a hydrolyzed condensate of alkyl silicic acid, particularly tetralower alkyl (methyl, ethyl) silicic acid.

And the colloid particle size is 30 to 100, especially 50
It is said to be around 80 people.

Moreover, alcohol, especially one aliphatic alcohol, alkyl acetate, or a mixed solvent of these and an aromatic hydrocarbon can be used as the solvent.

For hydrolysis, mineral acid is added as necessary.

Then, a stabilizer such as ethylene glycol, a surfactant, etc. are added as necessary.

An example of such a colloidal particle dispersion is one in which silicon tetrachloride (Si0 Bun 4) and a monohydric aliphatic alcohol are dissolved in acetic acid alkyl ester, which is described in Japanese Patent Publication No. 31-6533. Then, a base layer consisting of this coating film is formed, and a recording layer is coated on this base layer. A solution containing alcohol, alkyl acetate, and a mineral acid with 1 to 20 wt% of ethylene glycol added thereto may also be used.

Furthermore, an alcohol solution of tetra-lower alkyl silicic acid described in Japanese Patent Publication No. 45-35435 may also be used.

In such cases, monohydric aliphatic alcohols to be used include methyl alcohol, ethyl alcohol, denatured alcohol, improlyl alcohol, butyl alcohol, or their mixtures, and alkyl acetates include methyl acetate, ethyl acetate, and acetic acid. Amyl, butyl acetate, or a mixture thereof may be used, and as the mineral acid, hydrochloric acid, sulfuric acid, etc., which are used industrially, may be used.

Incidentally, these dispersions may be applied by spinner coating or the like according to a conventional method.

Then, drying may be performed at 40 to 80°C for about 20 minutes to 2 hours.

The coating film thus formed is a red silicon oxide coating 11.

The thickness of the stratum is approximately 0.005 to 0.05 km. Particularly preferably, the thickness of the melon is about 0.08 to 0.012 m.

If the depth of the stratum exceeds 0.051 Lm, the precloop will be buried and no tracking signal will be obtained.

Normally, a recording layer is directly formed on such an underlayer, but if necessary, in some cases, another intermediate layer may be formed between the underlayer and the recording layer. You can also.

In addition, on the recording layer, if necessary, each 111I uppermost protective layer, which functions as a back surface when using a transparent substrate,
It is also possible to provide a single layer of half-mirror.

However, it is preferable not to stack the reflective layer.

The medium of the present invention is prepared by placing the layers having the above-mentioned recording layer on one surface of such a substrate so as to face each other with a predetermined distance between them, and sealing the substrate to prevent dust. It can also be used to prevent scratches.

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

At this time, due to the heat generated by the dye in the recording layer, the self-acidic resin decomposes or the thermoplastic resin and the dye melt, forming pits.

In this case, writing is preferably performed from the gas back side.

In particular, when a tri- or tetracarbocyanine dye is used, extremely good writing can be achieved when a recording semiconductor laser diode with a wavelength of 750.780.830 n++ is used.

In addition, when using phthalocyanine dye, 730~
When using a recording semiconductor laser diode with a wavelength of 760 nm, very good writing can be performed.

The pits thus formed are read out by detecting reflected or transmitted light, especially reflected light, of the readout light of the above wavelength while the medium is running or rotating.

In this case, it is preferable that the readout light is irradiated from the back side of the substrate and the reflected light is detected.

Note that when a thermoplastic resin is used for the recording layer, the pits once formed in the recording layer can be erased with light or heat and then rewritten.

Furthermore, a He--Ne laser or the like can also be used as the recording or reading light.

■Specific Effects of the Invention If the underlayer of the present invention is formed between the substrate and the recording layer, the deterioration of the resin substrate caused by the melt for coating the recording layer will be extremely small, so the decrease in reflectance of the recording layer will be minimal. , the read S/N ratio is significantly improved.

Furthermore, there is no deterioration in reflectance over time due to storage.

In this case, such effects are extremely high compared to the case where another base layer or a silicon oxide base layer made of a solution coating film or a vapor deposited film is provided.

The present inventors conducted various experiments to confirm the effects of the present invention.

An example is shown below.

Experimental Example 1 A dye (D), a resin (R), a quencher (Q), and a quencher-dye conjugate shown in Table 1 below were used in a predetermined solvent at the quantitative ratio shown in Table 1. Dissolved in diameter 3
A recording layer of 0.07 gm was formed on a 0c+s acrylic disk substrate (polymethyl methacrylate of MFI=2) to obtain various media.

In this case, in the medium of the present invention, an underlayer was interposed between the recording layer and the substrate.

For the base layer, mix ethyl acetate and ethyl alcohol in a ratio of 10:11.
While stirring, gradually add 5t (OC2H5
) After adding 4 to ethyl acetate at a ratio of 2/25, 3 to
The solution left for 4 days was further diluted 10 times with n-propertool, and then a coating layer was formed on the substrate by processing at 60° C. for 30 minutes.

In this case, the particle size of the silicon oxide colloid was 50-80.

The film thickness of the base layer is approximately 0.08 JLm, 0.08 JLm in the present invention.
For comparison, a case without an underlayer and a very thin underlayer with a thickness of 0.005 mm were used. For further comparison, a propatool solution of tetraethoxysilane was applied.

A sample was obtained in which a base layer of 0.01 μm was formed.

In addition, in Table 1, N and C have a nitrogen content of 11.5 to 12
．． 2%, nitrocellulose with a viscosity of 20 seconds according to JIS K6703.

Using the above samples, the C/N ratio was determined to be 1111.

The results are shown in Table 1.

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

Applicant TDC Co., Ltd. Agent Patent Attorney Akira Ishii - Continued from page 1 O Inventor Takahashi - Husband [Partner] Inventor Kuroiwa Request 1-1, Nihonbashi, Chuo-ku, Tokyo Inside TDC Co., Ltd. TDC Co., Ltd., 1-1, 1-1, Nihonbashi, Chuo-ku, Tokyo

Claims (1)

[Scope of Claims] (1) A base layer made of a coating film of a colloidal particle dispersion of a silicon-based condensate is provided on a resin substrate, and a record made of a pigment or a pigment composition is provided on the base layer. An optical recording medium characterized by having a layer. (2) The optical recording medium according to claim 1, wherein the substrate is substantially transparent to writing light and reading light. (3) The optical recording medium according to claim 1 or 2, wherein the substrate is made of acrylic resin or polycarbonate resin. (4) The optical recording medium according to any one of claims 1 to 3, wherein the dispersion medium of the colloidal particle dispersion is alcohol, alkyl acetate, or a mixed solvent thereof. (5) The optical recording medium according to any one of claims 1 to 4, wherein the silicon-based condensate is a hydrolyzate of silicon halide or alkyl silicone distillate. (6) Colloid particle size is 30 to 100 4, ¥
An optical recording medium according to any one of claims 1 to 5. (7) The optical recording medium according to any one of claims 1 to 6, wherein the underlayer has a thickness of 50 to 500 layers. (8) The recording layer is made of a dye composition, and the dye composition is
The optical recording medium according to any one of claims 1 to 7, containing a dye and a resin. (9) The recording layer is made of a dye composition, and the dye composition is
An optical recording medium according to any one of claims 1 to 8, which contains a dye and a quencher. The optical recording medium according to any one of claims 1 to 9, wherein the (IO) dye is a cyanine dye or a phthalocyanine dye. (11) The optical recording medium according to any one of claims 1 to 10, wherein the quencher forms an ionic bond with the dye. (12) The optical recording medium according to any one of claims 1 to 11, in which recording and reading are performed from the back side of the substrate. (13) The optical recording medium according to any one of claims 1 to 12, in which the recording layer is not laminated with a reflective layer.