JPS6236469A - Indolenine compound and optical recording medium containing the same - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I, wherein Y is H, Cl; R is a group of formula II (wherein l is 0.1; m, n are each 1,2; R<1> is a 1-4C alkyl); A is a group of formula III or IV (wherein B is Y or a group of formula V); X is an anion. EXAMPLE:Compound of formula VI. USE:Indelenine compds. which do not cause agglomeration nor crystallization during storage and lowering in a readout S/N ratio and are suitable for use as a material for an optical recording medium. PREPARATION:1 mol of a compd. of formula VII is condensed with 2mol of a compd. of formula VIII or IX (wherein D is a group of formula X) in the presence of a salt of a fatty acid (e.g. sodium acetate) as a catalyst in a dehydrating org. acid such as acetic anhydride or a mixture thereof with glacial acetic anhydride at 60-130 deg.C for 10-60min. If desired, the product is recrystallized from an alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to indolenine compounds and their uses. More specifically, the present invention relates to a novel indolenine compound and an optical recording medium containing the same.

"Prior Art" In recent years, various attempts have been made to put optical recording media using organic compounds into practical use instead of optical recording media using metal compounds. For example, a thin film of organic dye is formed on an organic or inorganic substrate to form an optical recording layer, and a part of the recording layer is melted or removed according to a number signal using recording light such as a laser to form so-called bits. Attempts have been made to write a recording signal and to irradiate a reading light onto the recording layer to which the recording signal has been applied in this way, thereby reproducing the recorded signal. Indolenine dyes exhibit strong absorption and high reflection of near-infrared light, for example, light in the range of 750 to 8701 m, and are therefore attracting attention as compounds suitable for such purposes. For example, in the known optical recording medium using an indolenine dye in the optical recording layer described in JP-A-59-81194, the indolenine dye forming the optical recording layer aggregates and crystallizes during storage. Readout signal to noise ratio (hereinafter referred to as S/N)
The disadvantage is that it lowers the ratio. Such a phenomenon is particularly likely to occur when the recording medium is stored at high temperature or under high temperature and high humidity conditions after writing has been performed on the optical recording layer.

"Problems to be Solved by the Invention" It is desired to develop an optical recording medium that does not cause aggregation or crystallization of organic dyes in the optical recording layer during storage, which will not cause a decrease in the readout S/N ratio. .

"Means for Solving the Problems" The present inventors have conducted extensive research in order to find the above-mentioned organic dye-based optical recording medium, and as a result, they have arrived at the present invention. That is, the present invention is based on the formula % formula % [In formula (1), Y is a hydrogen atom or a chlorine atom, and R is + (
CH2)m 0-)1 (CHz)n OR' (I stands for O or 1, m and mouth each independently stand for 1 or 2, R
1 represents a carbon chlorine atom or -Ne)2] respectively, and X represents an anion] and an optical recording medium containing the same are provided.

The indolenine compound represented by formula (1) can be prepared by various methods, but it is convenient to prepare it by the following method.

That is, 1 mole of the compound represented by formula (2) (in formula (2), R and Y represent the same meanings as above) and formula (3) or (3) (formula (3)
), B represents the same meaning as above.

In Bunbu (3), D is -NH (◇ stands for table) 2 moles of the compound is mixed with acetic anhydride or a mixture of acetic anhydride and glacial acetic acid in the presence of a fatty acid salt catalyst such as sodium acetate or potassium acetate. For example, 60-1 in a dehydrating organic acid such as
It is produced by condensation under condensation conditions such as at 30°C for 10 to 60 minutes. The product is purified by recrystallization in an alcohol such as methanol or ethanol, if necessary.

Specific examples of the indolenine compound represented by formula (1) include the following compounds.

In the table, Y, R and X- are in formula (]).

] HCH2OCH3a ClO4-2H-
cH20C4H9bC1 3H-C2Fi40CH3e Cl04-4
HC2Ha ocL c CI O4 compound so Y RA X1 number 5 H-C2H40C2H5I-6H-C2H4
0C2H5d BF4-7 H-C2H40C2
H5e C104-8t (C2H40C4H9CC
2H55O4-9CI -CH20C3H7a C
H345O3-10CI -C2H40CH3b B
F411 CI C2H40CH3eC10412
CI C2H40C2H5f ClO4] 3
CI C2H40C4H9Cl-14HCH
20CH20CH3b ClO4]5H-CH
20CH20C4H9f C10416H-CH20
CH20CH3b I-17H-Cf(zOc2
fLOc4H3b C2H55O4-]8H-c2
H40CH20CH3aCIO4] 9 HC2H4
0CHzOC2Hs e C10420H-CzH
40C2HaOCzH5b BF42] H-C2
H40C2H40C2H5e C10422CICH
20CH20CH3c CI-Compound So Y
R, A X1 number 23 C1-CH2oc2f (40C2H5f l
-24CI-C2H40CH3 investigation C4H8d, B
F4-25 CI-C2H40C2H40C2H5
e C104-26CI ('2H40C2H40C
2H5b ClO4 - a, b in column A in the table above
, c, d, e, and f are the following compounds of the present invention, for example, in dichloromethane, they have an extremely thick absorption wavelength in the range of 770 nm to 810 nm, high molecular absorbance (ε), and good solubility in organic solvents, so they can be used as near-infrared absorbing dyes. The value is different. Although the compounds of the present invention are useful for various filters utilizing such near-infrared absorption ability, they are especially valuable as dyes for optical recording media.

The optical recording medium containing the indolenine compound of the present invention is usually produced as follows.

An indolenine compound of formula () is dissolved in a solvent, applied onto a substrate, and dried. If necessary, a resin binder or a singlet oxygen quencher such as a metal complex salt of acetylacetone can also be added thereto. Examples of the solvent used include dichloromethane, dichloroethane, acetone methyl ethyl ketone, etc., but ethanol is preferred.

The method of application is to dissolve the compound of formula (1) in a solvent, mix and dissolve an appropriate amount of singlet oxygen quencher if necessary, and apply the mixture over a distance of 10 to 1000 m using a spray or spinner.
It is preferably applied to a thickness of 30 to 70 nm. When using a -1 term oxygen quencher, the addition ratio is 0.05 to 5.0, particularly 0.2 to 1.0, relative to compound 1 of formula (1).
The range is 5.

The material of the substrate forming the recording layer is not particularly limited and may be any of various resins, glass, ceramics, metals, etc. However, there are certain issues such as molding of the substrate, difficulty in handling, storage stability, prevention of dye migration to the substrate, etc. An acrylic resin board or a polycarbonate wood resin board is preferred.

As a light source for recording and reading, it is convenient to use a near-infrared laser, for example, a semiconductor laser beam of 8300 m.

"Example" The present invention will be explained in more detail with reference to Examples.

Example 1゜Additionally 1.60% aqueous HC104 solution in 15 ml of acetic anhydride.
A mixture of 7 g was added thereto, refluxed for 15 minutes, and then cooled to room temperature. 50 ml of water was added to this and the resulting resinous product was separated by decantation. By crystallizing this from methanol, 1.2 g of the following indolenine compound was obtained. (mp193℃) λmax-787nm, t 340,000.(
(in dichloromethane) Example 2゜Example 1 and 2 were treated in almost the same manner as in Example 1 and 2 except for Example 2.
g of the following indolenine compound was obtained.

(m9188°C) λmax 796 nm, ε 320000 (in dichloromethane) Example 3° A mixture consisting of 3.0 g of CH3CO0K and 20 ml of acetic anhydride is stirred and reacted at 95-100°C for 15 minutes. After cooling, 100 ml of water was poured and the resulting resinous product was separated by decantation. By recrystallizing this from methanol, 4.5 g of the following indolenine compound was obtained.

mp 210°C λmax 803 nm, t 350000 (in dichloromethane) Examples 4 to 26° In each example, indolenine compounds having the above compound numbers were prepared and the λmax in dichloromethane was measured.

(by weight) was dissolved in 100 parts by weight of dichloroethane (9 parts by weight), and the λmax of the acrylic substrate (acrylic light MR recording layer) was measured. At 8400 m, it was shifted to a longer wavelength by about 5 Q nm than the value measured with the dichloromethane solution. A signal was recorded on this recording medium using a semiconductor laser with a wavelength of 830 nm, a narrow beam diameter, a linear velocity of 1.2 m/s6C, a writing power of 5 mW, and 0.7 MHz.

As a comparative compound (compound described in JP-A-59-81194), an optical recording layer was prepared in the same manner as above, and signals were recorded.

When the surface of the optical recording medium (optical disk) on which these recordings were recorded was observed using a scanning electron microscope, clear pits were observed. Furthermore, when a low-output 8301m semiconductor laser was incident on each of these optical recording media and the reflected light was detected, a waveform with a high S/to ratio was obtained.

])1100 for each optical disk on which a signal has been recorded.
Heat resistance and 4 heat loss tests were conducted at 260°C and 90% RH. ]) and 2) in the optical recording medium using comparative compound (4) when observed with a scanning electron microscope.
Under both conditions, crystallization occurred over the entire surface of the recording layer, and the formed bits were extremely unclear. On the other hand, in the optical recording medium using the indolenine compound of compound number 3, no change in the surface of the optical recording layer was observed under both conditions 1) and 2), and the S/N ratio of the optical disc was 5. After several days, the results of the heat resistance test showed that a few crystals were observed under a scanning electron microscope, and the decrease in the S/N ratio was extremely small. In the moist heat resistance test after 5 days, slightly more crystals were observed by scanning electron microscopy than in the heat resistance test, but the decrease in the 8/N ratio after the heat resistance test was extremely small.

Example 28. Optical recording media were produced in the same manner as in Example 27 using the indolenine compounds of compound numbers 4, 7, 10 and 2, and signals were recorded. Furthermore, heat resistance and moist heat resistance tests were conducted under the same conditions as in Example 27, and when observed with a scanning electron microscope after 5 days, there was little change in the recording layer due to crystallization of the indolenine compound, and almost no decrease in the S/N ratio was observed. I couldn't.

``Effect of the invention'' During storage, the compound aggregates and crystallizes, causing readout S
An organic compound (indolenine compound) for optical recording media was obtained that does not have the disadvantage of causing a decrease in /N ratio.

Claims (1)

[Claims] 1. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In formula (1), Y is a hydrogen atom or a chlorine atom, and R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( l represents 0 or 1, m and n each independently represent 1 or 2, R^1 represents an alkyl group with 4 or less carbon atoms), A is ▲A mathematical formula, a chemical formula, a table, etc.▼ or ▲ Contains mathematical formulas, chemical formulas, tables, etc.▼
(In these formulas, B represents a hydrogen atom, a chlorine atom, or ▲a mathematical formula, a chemical formula, a table, etc.) respectively, and X represents an anion] Compound 2, formula ▲a mathematical formula, a chemical formula, There are tables, etc. ▼ (1) [In formula (1), Y is a hydrogen atom or a chlorine atom, R is ▲ Numerical formula, chemical formula, table, etc. ▼ (l is 0 or 1, m and n are each independently) 1 or 2, R^1 each represents an alkyl group with 4 or less carbon atoms), A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In these formulas, B represents a hydrogen atom, a chlorine atom, or ▲represents a mathematical formula, chemical formula, table, etc.), respectively, and X represents an anion] An optical recording medium characterized in that it contains a compound represented by the following.