JPS61239443A - Optical disk and optical recording method - Google Patents

Abstract

PURPOSE:To enable the recording of CD format signals and CD-ROM signals by forming a recording layer with a coated film contg. an indolenine cyanine pigment and a bisphenyl dithiol transition metal complex. CONSTITUTION:A coated film contg. an indolenine cyanine pigment and a bisphenyl dithiol transition metal complex is used as the recording layer of an optical disk. Since such a coated film is used as the recording layer, >=60min maximum recording time can be obtained, when a binary digit string having 0.84-3.6mum length and 0.84-3.6mum interval at 1.2-1.4m/sec linear velocity is recorded in high density. Moreover, high sensitivity can be obtained because an indolenine cyanine pigment is used. Furthermore, the disk is not deteriorated by many-times reproduction, since the bisphenyl dithiol complex is contained in the composition.

Description

[Detailed Description of the Invention] ■ Background Technical Field of the Invention The present invention relates to an optical disc, particularly an optical disc for DRAW (direct read after write) compatible with CD (compact disc) or a DRAW compatible with CD-ROM (read only memory), and this optical disc. CD format or CD-ROM format using
□ Concerning optical recording methods of signals.

Prior Art and its Problems Compact discs (CDs) are becoming widely used for audio, especially music playback.

In this CD, a bit string containing EFM digital audio signal (CD format signal) information is formed on the base surface of a transparent resin such as polycarbonate during injection molding, and a reflective thin film such as AfL and a protective film are applied on this. A laser beam is irradiated from the back side of the base, and the CD format signal of the bit string is read from the change in reflectance caused by the unevenness of the pits, and music is played back.

There is a CD standard for such CDs, and according to this standard, the inner diameter of the signal surface is 45 mmφ, and the outer diameter of the signal surface is 116 mm.
By rotating at a constant linear velocity of 1, 2 to 1, 4 m/Sec at mmφ, bit width of 0.8 lm, track pitch of 1.6 m, the maximum recording time is 63 to 74 minutes. must be obtained.

However, such conventional music playback CDs are currently only for playback, cannot record, do not have so-called DRAW functions, and cannot be edited.
Adding functionality is an issue. In addition, CD-ROM compatible discs are required for files such as various documents, data, and still images, and DR to these CD-ROMs is required.
The provision of AW function is long awaited.

By the way, as an optical recording medium having a DRAW function,
A phase-transition type recording layer using a Te-based chalcogenide or the like and causing a crystalline-amorphous transition by recording light to form a recording point.

Various proposals and practical applications have been made, including a pit-forming type in which pits are formed by irradiating a Te-based or organic-based film with recording light and melting or removing the irradiated area.

However, with general optical recording media such as Te-based, recording and reproduction with sufficient characteristics cannot be achieved unless the linear velocity is increased and the pit gap is widened. There is an inconvenience that recording cannot be performed on CDs and CD-ROMs that use this recording method.

(2) Object of the Invention An object of the present invention is to provide a DRAW type optical disc and an optical recording method on which CD format signals and CD-ROM format signals can be recorded.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the first invention has a recording layer on a substrate, 1,
While rotating at a constant linear velocity of 2 to 1,4 m/Sec, a CD format signal or CD-
The present invention is an optical disc for recording ROM format signals, characterized in that the recording layer is a coating film containing an indolenine cyanine dye and a bisphenyldithiol transition metal complex.

Further, the second invention provides an optical disc having a coating film containing an indolenine-based cyanine dye and a bisphenyldithiol transition metal complex as a recording layer on a substrate.
While rotating at a constant linear speed of m/sec, recording light is irradiated onto the recording layer to create a length of 0.
．． A bit string of 84 to 3.6 lumens and a gap of 0.84 to 3 µm is formed to generate a CD format signal or CD-
This is an optical recording method characterized by recording a ROM format signal.

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

The optical disc of the present invention has a recording layer on a disc-shaped base made of a resin material.

The base size is according to the CD standard: outer diameter 120mmφ, inner diameter 15mmφ, base thickness 1.2mm, total disk thickness 3mm.
The following are preferred.

The resin material to be used may be acrylic resin, polycarbonate resin, nylon, epoxy resin, etc., provided that it is substantially transparent (preferably 80% or more transparent) to recording light and reproduction light. It is preferable that there be.

It is preferable that tracking grooves be formed on the recording layer forming surface of such a substrate.

The depth of the groove is approximately 1/8n, particularly 1/7n to 12n (where n is the refractive index of the substrate), and the width of the groove is approximately the track width. It is said that

It is preferable that writing light and reading light are irradiated from the back side of the substrate, using the recording layer located in the concave or convex portions of the groove as a recording track section.

With this configuration, the writing sensitivity and the reading S/N ratio are improved, and the tracking control signal is also increased.

The recording layer of the present invention consists of a coating film containing an indolenine cyanine dye and a bisphenyldithiol metal complex.

By using a coating film of such an indolenine cyanine dye composition as a recording layer, 1, 2 to 1, 4
At a linear velocity of m/Se C, the length is 0.84~
When recording bit strings at a high density of 3.6 pm and an interval of 0.84 to 3.6 JLm, a maximum recording time of 60 minutes or more can be obtained.

In contrast, such recording is not possible with conventional various recording layers. Furthermore, since the present invention uses an indolenine cyanine dye, the sensitivity is extremely high compared to the case where a normal dye is used.

Furthermore, since a bisphenyldithiol complex is contained in one composition, it does not deteriorate even after being regenerated many times.

Among the indolenine cyanine dyes used, the following formula CI
) are preferred.

Formula CI) Φ-L='l' (X-)m In the above formula (I),! and Φ represents an aromatic ring such as an indolenine ring to which a benzene ring or the like may be fused.

These Φ and weight 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.

As the skeletal rings of these Φ and ψ, the following formula [Φ]
It is preferable that it is represented by ~[Φ■].

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

In these various rings, the group R1 bonded to the nitrogen atom in the ring is a substituted or unsubstituted alkyl group or aryl group.

Groups R1, R,' bonded to the nitrogen atom in such a ring
There is no particular restriction on the number of carbon atoms in this group. In addition, when this group further has a substituent, examples of the substituent include a sulfonic acid group, an alkylcarbonyloxy group, an alkylamido group, and an argylsulfonamide group. , 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, at the 3rd position, there are two substituents R2.

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, and among these,
Preference is given to unsubstituted alkyl groups having 1 or 2 carbon atoms, especially 1.

On the other hand, Φ and! At a given position in the ring represented by
Furthermore, other substituents R4 may be bonded. Examples of such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and alkyl groups. Carbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamido group, arylamido group, alkylcarbamoyl group, arylcarbamoyl group, alkylamino group, arylamino group , a carboxylic acid group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, a nitro group, etc. .

And the number of these substituents (p, q) is usually
0 or about 1 to 4. Note that when p and q are 2 or more, the plurality of R4s may be different from each other.

This is because those having an indolenine ring have excellent solubility in solvents, coating properties, and stability, exhibit extremely high reflectance, and have an extremely high readout S/N ratio.

On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye;
It is preferable that it is any one of I) to (LIK).

Formula (LI) 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 alkoxy group such as a methoxy group, a dimethylamino group, a diphenylamino group, a methylphenylamino group, a morpholino group, an imidazolidine group, and an ethoxycarbonylpiperazine group. Preferable examples include di-substituted ami7 groups such as groups, fulkylcarbonyloxy groups such as acetoxy groups, furkylthio groups such as methylthio groups, cyano groups, nitro groups, and halogen atoms such as Br and C1.

In addition, among these formulas (LI) to (LI)0, the tricarbocyanine linking group, especially formula % formula %. -, BF4-.

CH30303-, CfLO3O3- etc. can be mentioned.

Note that m is O or 1, but when m is O, R1 of Φ usually has one charge and becomes an inner salt.

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

1 block, ov Beni
1L engineering J3Di (ΦI) CH3C
H3O2(ΦI) CH3CH3O3(ΦI
) C2H40HCH3O4 (Φwork) (3:7=to 83:Na" CH3O5(ΦII)
CI(3CH3O7(9m) CH
2, CH20HCH2O8(OH) (CH2
)2 0COCH3CH3O9 (9m) (C
H2) 2 0COCH3CH3010 (9m)
CH3・CH3010(
Φnl) CH3CH3O12 [ΦI)
C, 8H37CH3013 (ΦI)
C4H9CH3LL Dan-Yi
x-(Ln) HI-(Lm) H0 sentence 04- (L
m) HI Br-(Ln)
H- -(Lm) HClO4-(Ln)
H- -(Lff) HClO4-(LH)
HBr (Lm) -N (Ca Hs)2 1
Cl0a-(LH) H0 sentence 0
4(Lm)-N(CaHs)2
1 0 sentence 04- (Lm)
HI-(LII) HCl0a color imperial, earthwork j u3014
(ΦI) C8HIG 0COCH5C
H3O15 [ΦI) C7HgCH20H, CH
301B (Φ■) CB H17CH
3O17 (9m) CIIH17CH3C7H1
4COO-CH3 O18 (Φ■) (C7H, C00HD19
(O ■) C7H14COOC2H5CH3O
20[:Om) Ca Hg
CH3021 (ΦIII) Cl8
H3? CH3O22 [ΦI
n) C4H9CH3O23 [ΦI) C
l7H34COOCH3CH3O24(OI)
C3HIGOCOCHC) (3D25 [ΦI)
C8HI7 C2H
5D2B [ΦI] C7HI5
C2H5LtL--Goichi
Also -X--(Lm) -N(C8H5)2
1 ClO4-(Ln)
H1-(LII) HClO4-(Ln)
H- (LI[I]-N N-COOC2Hs 1
-1 (LII) HBF4
- (Lm) -N(C8H5)2
1 ClO4-(LII)H
0 sentence 04- (LII) HC
Also 04- (Lll) HI(
Lm) -N (C6Hs) 2 1
I-(LII) HI-(LII) HI L1 addition, immun-'l' jLL
LLJ3D27 [Φ■) C
17H34COOCH3CH3D28 [ΦII]
Ca H+s CH20COCH3CH3D'
! 9 (ΦII) C17H3S
CH31) 30 (OII)
C7HI3 COOCH3C2HaD31
[Φm] C7HI4CH20HCH3D3
2 [Φm] C7HI3 CH20COC2
H5CH3D33 [Φm] C17H34
COOC2H5CH3D34 [Φm]
C17H3S' CH3D3
5 (Om) C7H2S
C2H5D38 (ΦrV)
CH3CH3D37 [Φff]
CH3CH3D38 [ΦrV] C4H
g CH3D39 [
ΦIV) (CH2)2 0COCH3CH3jL
IL--E RX--(LII) H0 sentence 04 (Lm)
-N N-COOC2Hs l I(
LIV) -N N-COOC2Hs l
C view 04- (L■)
HC Mi04- (LII)
HCJ104- (LII)
HI-(Lf[[]-N(C8H5)2
1 1- (LIT)
HI I-(LII)
H1-(LII) HI--(LI
E) HC! ;L04- (L
ff) H0 sentence 04- (LI
I) H1 Color Processing Δ, Immunity-v7e'lL-''3D41 (ΦI)
CH2G)12 0HCH3D42 [Φm]
CH3CH3D43 [ΦI]
CH3CH3D44 [ΦII
CH3CH3D45 [ΦI]
CH3CH3, C2HsD4B [ΦI]
CH3CH3D47 [ΦI]
CH3CH3D4B [ΦI]
CH3CH3D49 [ΦI] CH
3CH:s-l1 l--E-mX-
-(L■) HBr (Lm) Br I
CJ104- (LW)
H-C1o4- (Lm) H
-Cl0a-(L■) H-Cmata045
-0 sentences [L■) H-CfL045
．． 8-C1(LII) H-CfLO4
5-OC2Hs (LII) H-C
Also 045-CH3C0NH (LII)
H-C104 Koman, Men, j 1 upper f'
R3-1 work 050 (ΦI)
CH3CH35,7-CID51 (ΦI)
CHa CH35, 7-C2
H500CD52 [ΦI) CH3
CH35,7-CH3025D53 [ΦI]
CH3CH35,7-CH5D54 [
ΦI) CR3CR35,7-CH5C
ONHD55 [ΦI] CH3CH
3B-CH3C0NHD58 (ΦI)
C2R5CH35,1-CH3025D57
[ΦI) CH3CH3HD58 [
ΦI) CHa C
Ha HD58 [ΦI]
CH3CH3HD80 ((II)
CH3CH35,7-CH302SDEII
(ΦI) CH3CH35-C2H3
O0CD62 [ΦI] CH3CH
35-CH31--E M
L ■) H-CJLO4 CLn'J H-Cl04 (LII) H-Cl04 (LU)
H-CfL O4(Lll)
H-C! L04 (Lm) H-0 sentence 04 (Lf[[3N (Co Hs) 2 1
0 sentence 04 (Lm) N (C8R5) 2 1
Cn0a) L, m, )=R・=B r ,
IClO.

(LII) C1' Cf
LOa (Lll) H-0 sentence 04 (Lm)
H-C Mi04 (LII) H-CJIO4 The above cyanine dye can be easily synthesized according to the method described in Nitrogen-Containing Heterocyclic Compound Engineering, Dai Organic Chemistry (Breakfast Shoten), page 432, etc. .

That is, first, the corresponding Φ'-CH5 (Φ' represents the ring corresponding to the above Φ) is
, I (Rt is an alkyl group or an aryl group) to introduce R1 into the nitrogen atom in Φ' to form Φ-CH
5I- is obtained.

Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde, unsaturated hydroxyaldehyde, pentagencial or isophorone using an alkali catalyst such as piperidine or trialkylamine, or acetic anhydride.

Such a recording layer further contains a quencher.

This reduces reproduction deterioration and improves light resistance.

The quencher used is a bisphenyldithiol complex represented by the following formula -R'- Here, R5 to R8 are hydrogen, an alkyl group such as a methyl group or an ethyl group, a halogen atom such as Cl, or a dimethylamino group. , represents a substituted amino group such as diethylamino group.

M represents a transition metal atom such as Nf, Co, Cu, Mn, Pd, or Pt.

Furthermore, M in the above structure has a single charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion, and further, other ligands may be bonded above and below M. , Examples of this include the following:

σ σ σ σ σ σ σ σ σ σ, 1-1
---m--“- 1EZ 2 2 222 χ Z Z
σ C7d σ σ σ σ σ σ
σ These clenchers are 0.01 per mole of dye.
It is contained in an amount of about 12 moles.

Furthermore, the recording layer contains various resins, such as self-oxidizing resins such as nitrocellulose, depolymerizable resins such as polyα-methylstyrene, and thermoplastic resins such as polystyrene, nylon, and coumaron-indene resin. It may be contained.

Note that the recording layer further contains other dyes and quenchers.
Alternatively, various plasticizers, surfactants, antistatic agents, stabilizers, crosslinking agents, etc. may be contained.

The recording layer can be made of ketone type, ester type, ether type,
Coating such as a spinner coat may be performed using an aromatic solvent, a halogenated alkyl solvent, an alcohol solvent, or the like.

It is particularly preferable that such a recording layer has a thickness of 0.05 to 0.1 μm.

Depending on the recording layer thickness, the above-mentioned CD or CD-ROM
It is possible to record format signals.When coating the recording layer, the viscosity of the coating solution should be 0.5~
1Ocp, spinner rotation speed is 500~1.00Or
Approximately pm.

Various underlayers may be formed between such a recording layer and the substrate in order to prevent damage to the substrate due to the coating solvent.

Note that it is preferable not to form a top coat film on the upper layer of the recording layer.
Recording of OM format signals becomes even easier.

The optical disc of the present invention has a recording layer sealed to prevent dust and dirt from adhering to it.

In this case, the recording layer is sealed with voids. ° This void prevents a decrease in sensitivity.

It is sufficient that the gap length is equal to or greater than the depth of the tracking groove described above, but it is usually 0.1 mm or greater.

In order to seal the recording layer in this way, it is possible to integrate a protective plate or protective film onto the substrate having the recording layer so as to create a void above the recording layer, or to seal a pair of substrates having the recording layer with each other. They may be integrated so that the recording layers face each other with a gap between them.

In addition, when sealing, it is preferable to provide a ventilation hole and arrange a filter or the like in this ventilation hole.

To perform optical recording using such a RAW type optical disc, the following procedure may be performed.

Recording is normally performed from the back side of the substrate.

Recording usually uses a semiconductor laser of 750 to 850 nm. In the present invention, the recording power is 2 to 7 mW.
It is possible in the range of , and has extremely high sensitivity.

When recording, hold the disc at 1°2~l. 4m/s
e Rotate at a constant linear velocity of C.

And track width 0.81Lm, track 5.
Length 0-84~3.61Lm at pitch 1.6μm
, gap 0.84-3.6. A bit string of wm is formed as a spiral track.

At this time, with the EFM-CD format signal, recording for 60 minutes or more is possible with a signal surface having an inner diameter of 45 mmφ and an outer diameter of 116 mmφ.

Reproduction can be performed by detecting the reflected light from the semiconductor laser at the constant linear speed rotation described above.The reproduction power is 0.2~
The power should be approximately 0.7 mW.

Note that during recording, it is preferable to perform tracking control using the above-mentioned tracking groove.

■Specific Effects of the Invention According to the present invention, a DRA compatible with CD or CD-ROM
A W-shaped optical disc was realized, which is extremely advantageous for music editing and various files.

Furthermore, the sensitivity is extremely high.

Also, by playing it over and over again.

Recording signals do not deteriorate.

(1) Specific Examples of the Invention One specific example of the present invention will be shown below to explain the present invention in further detail.

Example 1. A photopolymer was coated to a thickness of 0.2 pm on an acrylic substrate with a thickness of 2 mm, an outer diameter of 120 mmφ, and an inner diameter of 15 mmφ, and a stamper was pressed onto it to cure it with ultraviolet rays, resulting in an outer diameter of 116 mmφ and an inner diameter of 45 mmφ. In the range of 0, 8
A spiral tracking groove having a width of 1 Lm, a depth of 0.07 μm, and a pitch of 1.6 JLm was formed.

On top of this, cyanine dye D2 and quencher Q8
(D:Q=5:2 (weight ratio)) was applied with a dichloroethane-cyclohexane 1:1 solution, and 0.06 ml of
A thick recording layer was formed.

Next, a protective film was formed on the surface of this disk so that a gap of 0.3 mm was present.

Using the optical disc produced in this manner, EFM-CD format signals were recorded at linear velocity recording power. The recorded bit string has a length of 0.9 to 3.31 Lm and a gap of 0.
．． It is 9 to 3.3 μm.

As a result, it was possible to record 68 minutes of EFM-CD format signals.

CD player, 0.5mW at linear velocity 1.3m/sec
FIG. 1 shows the reproduction pattern when reproduced with the reproduction power of .

In this case, the reproduction pattern changes in amplitude as shown in FIGS. 1 and 2 depending on the pit length and pit gap.

The degree of this change B/A (see Figure 2) was measured and found to be 0.69.

On the other hand, the reproduction pattern of a commercially available CD is shown in FIG. 3, the recording time was 68 minutes, and the B/A was 0.64.

In other words, the optical disc of the present invention is comparable to commercially available CDs.

When changing to Cu-phthalocyanine, good recording could not be performed with a recording power of 3.5 mW.

FIG. 4 shows a reproduction pattern when the recording power is 5 mW. B/A was 0965.

On the other hand, in the above case, when the recording layer was changed to a Te vapor-deposited film, reproduction was impossible at a linear velocity of 5 mW and 1.3 m/sec.

This Te film was heated at 5 mW, 1,6 m/S e
FIG. 5 shows the playback pattern when recording in C.

In this case, B/A was 0.50.

In addition, when we measured the number of times the signal level was repeatedly played until the signal level decreased by 10% while changing the playback power, the optical disc of the present invention was 106 times at 0°45mW, 0.5
The power consumption was 3×104 times in mW, and it was confirmed that there was very little reproduction deterioration.

From the above, the effects of the present invention are clear.

[Brief explanation of drawings]

FIG. 1 is a photograph substituted for a drawing of an oscilloscope waveform showing the signal reproduction pattern of the optical disc of the present invention, FIG. 2 is a diagram for explaining the evaluation of the signal reproduction pattern, and FIGS. FIG. 5 is a drawing-substitute photograph of oscilloscope waveforms showing signal reproduction patterns of a commercially available CD and two types of optical discs for comparison, respectively. Applicant TDC Co., Ltd. FIG, 1 FIG, 2 FIG, 3

Claims (1)

[Claims] (1) A recording layer is provided on a substrate, and a CD format signal or a CD-ROM format signal is recorded on the recording layer while rotating at a constant linear velocity of 1.2 to 1.4 m/sec. 1. An optical disc characterized in that the recording layer is a coating film containing an indolenine cyanine dye and a bisphenyldithiol transition metal complex. (2) While rotating an optical disk having a coating film containing an indolenine cyanine dye and a bisphenyldithiol transition metal complex as a recording layer on a substrate at a constant linear speed of 1.2 to 1.4 m/sec, a recording beam is emitted. is irradiated to form a pit row with a length of 0.84 to 3.6 μm and a gap of 0.84 to 3.6 μm on the recording layer to generate a CD format signal or CD-R.
An optical recording method characterized by recording an OM format signal.