JP3236951B2 - Optical information recording medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a write-once optical information recording medium in a heat mode.

[0002]

2. Description of the Related Art A compact disk type optical information recording medium is used as a means for recording and reproducing data such as images such as characters and figures or sound. This compact disc-based optical information recording medium has, for example, a recording layer made of an organic dye on a light-transmitting substrate, and irradiates this with a laser beam based on a data signal to raise the temperature of the cyanine dye.
This recording layer is deformed by melting etc. to form pits, and data is recorded, and the data is read by laser beam irradiation and read by the difference between reflected light from the pits and other parts and reproduced. You.

[0003] As organic dyes constituting such a recording layer, many dyes such as cyanine dyes and phthalocyanine dyes are known. For example, JP-A-3-73386 discloses a recording layer containing a cyanine dye in which an indolenine ring residue, a benzoindolenine residue or a dibenzoindolenine residue is linked by a methine chain for forming a cyanine dye. And an optical information recording medium having a high writing sensitivity, a good pit shape using a laser of 750 nm, 780 nm, 830 nm, etc., and a high reading S / N and C / N ratio. It states that an information recording medium can be obtained.

[0004]

However, as the recording wavelength of the laser becomes longer, the absorptance decreases and the sensitivity deteriorates. Therefore, when a cyanine dye specifically described in the publication is used, The sensitivity of the optical information recording medium is 7
At a wavelength of 90 nm or more, the recording power is required to be 9.0 mW or more.
It becomes larger than 0 mW and deviates from the standard.
There is still a need for an optical information recording medium that has insufficient performance, has higher sensitivity, has sufficient optical characteristics such as reflectance, and further reduces jitter.

A first object of the present invention is to provide an optical information recording medium having sufficiently high writing sensitivity and a sufficient degree of modulation. A second object of the present invention is to provide an optical information recording medium with sufficiently low jitter and more stable reproduction.

[0006]

In order to solve the above problems, the present invention provides (1) an optical information recording medium having a recording layer containing a light absorbing dye on a substrate, wherein the light absorbing dye is as follows: An object of the present invention is to provide an optical information recording medium containing a cyanine dye represented by the general formula [Chemical formula 1]. .

Embedded image (However, A is

Embedded image Or

Embedded image Where A ′ is

Embedded image ,

Embedded image Or

Embedded image Wherein R and R ′ are C _n H _{2n + 1} (n is 1 to 4), R ₁
Represents H, CH ₃ , Cl, OCH ₃ or OC ₂ H ₅ , and (R ₂ , R ₃ ) and (R ₂ , R ₄ ) each represent CH
₃ , Cl and OCH _{3 in the} group consisting of Cl and OCH ₃
Represents any of the same or two different combinations substituent except combinations, the combination comprises also the order is reversed, R ₅ represents -Cl, a -C H _3, X ^- is a halogen atom, an over Chloric acid, borofluoric acid, benzenesulfonic acid, toluenesulfonic acid, alkylsulfonic acid,
X represents an anion of benzenecarboxylic acid, alkylcarboxylic acid or trifluoromethylcarboxylic acid, and when R and R ′ have a group bonded to an alkali metal ion, X ⁻ may not be present. )

In the present invention, the cyanine dye represented by the above general formula [Chemical formula 1] is represented by the following general formulas [Chemical formula 9] and [Chemical formula 10] when A is more specific.

[0008]

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[0009]

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When A 'is made more specific, it is represented by the following general formulas [Formula 11] to [Formula 14].

[0011]

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[0012]

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[0013]

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[0014]

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From these, A and A 'are represented by the following general formulas.
When more specific, the general formula [Chem. 9]
Each combination of the general formulas [Formula 11] to [Formula 14],
The general formula [Chemical Formula 10] and the general formulas [Chemical Formula 11] to [Chemical Formula 14]
It is represented by each combination. In these equations,
R in the above [Formula 12]₁Is not H
The substituents and the like are the same as those of the above general formula [Chemical formula 1].
Is represented by the formula (R 1)_Two, R_Three),
(R_Two, R_Four) Is CH_Three, Cl and OCH_ThreeOr
Cl and OCH in the group consisting of_ThreeOptional except for the combination of
Represents a combination of two identical or different substituents of
The combination includes the case in which the order is reversed. "
When the combination of groups is (R_Two, R_Three), (R_Two, R_Four)
Then, each (CH_Three, CH_Three), (Cl, Cl),
(CH_Three, Cl), (Cl, CH)_Three), (CH_Three, OC
H_Three), (OCH_Three, CH_Three) Or (OCH_Three, OCH
_Three) In the above general formulas [Chemical Formula 13] and [Chemical Formula 14].
(R_Two, R_Three), (R_Two, R _Four) Also these combinations
Is indicated by Specific individual compounds are described in general terms above.
In each of the combinations of formulas, (R_Two, R_Three),
(R_Two, R_Four) Is selected from the above, and R_Five, X^-
Is determined by specifically selecting from the groups exemplified above.
However, preferred specific compounds are compounds shown in Examples described later.
And similar compounds.

A compound represented by the above general formula [Formula 1],
That is, the optical information recording medium using the compounds represented by the general formulas [Chemical Formula 9] to [Chemical Formula 14] can achieve the above object because of the unique characteristics of the compound and the laser light wavelength of 600.
Writing by ~ 810nm and laser light wavelength 770 ~
This is because the wavelength characteristics of reading at 810 nm are compatible with these compounds. In addition, as a synthesis method of these dyes, The Chemistry of Synth
The method described in etic Dyes Vol 14 can be used.

To manufacture the optical information recording medium of the present invention,
A dye solution is prepared by dissolving a cyanine dye represented by the above general formula [Chemical Formula 1], and this is applied to a light-transmitting substrate. This dye solution contains a fluorine-based solvent such as chloroform, dichloroethane, and fluorinated alcohol, methyl ethyl ketone,
Cellosolves such as dimethylformamide, methanol, toluene, cyclohexanone, acetylacetone, diacetone alcohol, methylcellosolve, dioxane and the like can be used. In this case, the mixing ratio of the cyanine dye is preferably 1% by weight to 10% by weight. Examples of the substrate used in the present invention include plastics such as glass, epoxy resin, methacrylic resin, polycarbonate resin, polyester resin, and polyvinyl chloride resin. Further, to apply the cyanine dye solution to the substrate, it is preferable to use a spin coating method. In this case, a conventionally used thickness of the coating layer after drying can be applied. Further, the recording layer applied in the present invention may contain other compounds such as a singlet oxygen quencher and a light absorber.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following embodiments.

[0019]

【Example】

Example 1 The following cyanine dye was mixed with 3 ml of tetrafluoropropanol.
Was dissolved to a concentration of 40 mg / μl, and the cyanine dye solution was applied on a polycarbonate substrate by spin coating to form a recording layer comprising a light-absorbing dye layer having an average thickness of 100 nm.

[0020]

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Next, a reflective layer of Au (gold) was formed on the recording layer by a sputtering method, and a protective layer composed of an ultraviolet cured film was formed thereon. In this way, an optical disc as a compact disc optical information recording medium is obtained. The optical disk was irradiated with a 795 nm laser from the substrate side to record an EFM signal. Also, this recorded optical disk is loaded on a commercially available CD player (Aure
x XR-V73), the modulation was 80
% And asymmetry were -5%, and the recording power at this time was 7.9 mW. At this time, the reflectance of the unrecorded portion of the 780 nm laser light incident from the substrate side is 75%.
Met. The 3T jitter average value at this time is 27
ns and 35 ns of the CD standard were sufficiently satisfied. In addition,
Table 1 shows the structure of the above [Chemical Formula 15] and the above test results.
In the table, “standard” means that the modulation degree is 70% or more, the asymmetry is −4 ± 4%, and the sensitivity is asymmetry (0 to 8).
%) And the recording power is 8 mW or less, 3T jitter: 35 n
Say the following.

Examples 2 to 8 In Example 1, the indolenine-based cyanine dyes described in the respective columns of Examples 2 to 8 of Table 1 are used instead of the indolenine-based cyanine dyes of the above-mentioned [Chemical Formula 15]. Each optical disk was prepared in the same manner except that (compounds belonging to the combination of the above-mentioned general formula [Chemical formula 9] and the general formulas [Chemical formula 11] to [Chemical formula 14]) were used. Are shown in the respective columns of Table 1.

Examples 9 to 14 In Example 1, the indolenine-based cyanine dyes listed in the respective columns of Examples 9 to 14 of Table 1 are used instead of the indolenine-based cyanine dyes of the above-mentioned [Chemical Formula 15]. (The above general formula [Chemical Formula 10] and the general formulas [Chemical Formula 11] to [Chemical Formula 1]
Each optical disk was prepared in the same manner as above except that the compound belonging to the combination [4]) was used, and the results of the same optical disk tests as in Example 1 are shown in the respective columns of Table 1.

Comparative Examples 1 and 2 In Example 1, the indolenine-based cyanine dyes listed in the respective columns of Comparative Examples 1 and 2 in Table 1 were used instead of the indolenine-based cyanine dyes of the above [Chemical Formula 15]. (A compound outside the scope of the present invention) wherein R ₅ is H in the combination of the above general formulas [Formula 10] and [Formula 11].
Each optical disk was produced in the same manner as in Example 1 except that the above was used, and the results of the same tests performed in the same manner as in Example 1 are shown in the respective columns of Table 2.

[0025]

[Table 1]

[0026]

[Table 2]

It can be seen that the optical disc of the above embodiment is superior to the optical disc of the comparative example in both the relationship between asymmetry indicating sensitivity and recording power. Based on these results and other factors described above, the invention of the present application is referred to as "optical information recording which has a recording layer containing a light-absorbing dye on a substrate and is capable of recording with a laser beam of 600 to 810 nm and reproducing with a laser beam of 770 to 810 nm. In the medium, the light-absorbing dye contains a cyanine dye (or an indolenine-based cyanine dye) represented by the following general formula [Formula 1], and the asymmetry by the laser light is in the range of -4 ± 4%; An optical information recording medium (or a compact disc optical information recording medium) whose modulation degree is not smaller than 70%, the recording laser power at that time is not larger than 8 mW, and the jitter is not larger than 35 ns. Further, in the invention of the present application, the “general formula [Formula 1]] is limited to a part of various combinations of the above general formula, or is limited to some or all of the cyanine dyes described in Examples and Preferred Examples. In all of them, a limitation may be added from the other items described above.

[0028]

According to the present invention, it is possible to provide an optical information recording medium having a high writing sensitivity, a sufficient degree of modulation, a sufficiently low jitter and a stable reproduction.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Emiko Hamada 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Yuden Co., Ltd. (56) References JP-A-4-201482 (JP, A) JP-A-4 JP-A-175188 (JP, A) JP-A-3-51183 (JP, A) JP-A-5-147356 (JP, A) JP-A-4-28588 (JP, A) JP-A-4-335221 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/26 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. An optical information recording medium having a recording layer containing a light absorbing dye on a substrate, wherein the light absorbing dye contains a cyanine dye represented by the following general formula [1]. Embedded image (However, A is Or And A 'is , Or Wherein R and R ′ are C _n H _{2n + 1} (n is 1 to 4), R ₁
Represents H, CH ₃ , Cl, OCH ₃ or OC ₂ H ₅ , and (R ₂ , R ₃ ) and (R ₂ , R ₄ ) each represent CH
₃ , Cl and OCH _{3 in the} group consisting of Cl and OCH ₃
Represents any of the same or two different combinations substituent except combinations, the combination comprises also the order is reversed, R ₅ represents -Cl, a -C H _3, X ^- is a halogen atom, an over Chloric acid, borofluoric acid, benzenesulfonic acid, toluenesulfonic acid, alkylsulfonic acid,
X represents an anion of benzenecarboxylic acid, alkylcarboxylic acid or trifluoromethylcarboxylic acid, and when R and R ′ have a group bonded to an alkali metal ion, X ⁻ may not be present. )