JPS62280263A - Cyanine dye - Google Patents

Abstract

NEW MATERIAL:Compds. of formula I (wherein R1 and R2 are each H or Cl; R3 and R4 are each methyl, ethyl or propyl; and X is an anion excluding the cases where R1 and R2 are the same groups and R3 and R4 are the same groups). EXAMPLE:A compd. of formula II. USE:Cyanine dyes suitable for use as mediums for record reproduction by laser beam, sensitized materials for copying and printing, sensitizing agents for sensitized materials and photographic silver salts, etc. and having max. wavelengths in the region of near-infrared rays. PREPARATION:An indolenium salt derivative of formula III is reacted with 1-anilino-5-anilinopenta-1,3-diene hydrochloride in an equimolar ratio. The resulting intermediate of formula IV is reacted with an indolenium salt derivative of formula V in an equimolar ratio.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a novel cyanine dye having a maximum absorption wavelength in the near-infrared region. The present invention relates to dyes that are particularly useful as materials for optical information recording media.

[Prior art]

Optical information recording media to which a thin film of cyanine dye is applied as a recording layer have been known (for example, in Japanese Patent Application Laid-Open No.
9-8579L). Recording media using this cyanine dye have a particularly large extinction coefficient compared to other dyes that absorb in the near-infrared region, so they have high sensitivity (recording/reproduction) and S/N, and they also have high storage capacity. It is a highly flexible optical information recording medium.

In addition, this recording medium can basically be formed by using various methods such as vapor deposition and coating to form a thin film containing cyanine dye on a substrate. It can be said that it is an industrially advantageous method, but
It requires a step of dissolving the cyanine dye in an organic solvent to form a solution. However, conventionally known cyanine dyes have low solubility in organic solvents and lack stability, resulting in poor dispersibility and stability of the cyanine dyes in the dissolution process, and recording media coated with these have poor recording reproducibility. The shelf life was insufficient.

〔the purpose〕

An object of the present invention is to provide a novel cyanine dye that has a maximum absorption wavelength in the near-infrared region and has excellent chemical stability and solubility in various organic solvents.

〔composition〕

According to the present invention, general formula (1) % formula % (wherein Ro and R2 represent a hydrogen atom or a chlorine atom,
R1 and R4 represent a methyl group, an ethyl group, or a propyl group, and X- represents an acid anion. However, the case where R1 and R2 are equal and R3 and R4 are equal is excluded. ) A cyanine dye is provided.

Examples of the acid anion in the above general formula (I) include halogen, alkyl sulfate, arylsulfonyl group, verchlorate, and tetrafluoroborate.

The cyanine dye represented by the general formula (1) of the present invention is:
It has maximum wavelength absorption in the near-infrared region, and is a chemically stable substance, as well as methanol, ethanol,
Alcohols such as isopropanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; and chloroform, 1,2-dichloroethane, Soluble in various organic solvents such as dimethylformamide and mixed solvents thereof.

Therefore, the cyanine dye of the present invention has the advantage that it can be used as a recording and reproducing medium using a laser beam, and can also be used as a sensitizing dye for photoreceptors or photoreceptors for copying and printing, and as a sensitizing dye for silver salt photography. It can also be used effectively as a material for optical filters, display materials, paints, etc.

The cyanine dye of the present invention can be synthesized by applying various production methods conventionally known in this field.1 The cyanine dye of the present invention is an asymmetric type in which the structures of the left and right indolenines are different. Since it is a pigment, it is synthesized in a two-step reaction. The first step is to react an indolenium salt derivative represented by the general formula (■) and 1-7nilino-5-anilinopenta-1,3-diene hydrochloride in an equimolar ratio as shown in the following formula, and Synthesize the intermediate shown in (m).

'711) Ba3 (m) The second step is shown in the following reaction formula, and the intermediate ([) synthesized in the first step and the indolenium salt derivative shown by the general formula (IV) are mixed in an equimolar ratio. The general formula of the present invention (
A cyanine dye represented by I) is produced.

(III)
(IV) (In the formula, R□ and R2 represent a hydrogen atom or a chlorine atom, R1 and R4 represent a methyl group, an ethyl group, or a propyl group, and X- represents an acid anion. However, R (Except when R2 is equal and R1 and R4 are equal.) Both of the above two steps are reacted at 70 to 120°C for 0.5 to 5.0 hours using acetic anhydride and alcohols as reaction solvents. When the solvent is acetic anhydride, the reaction rate can be accelerated by adding sodium acetate, and when the solvent is an alcohol, adding sodium acetate or a weak base such as a tertiary amine such as triethylamine or piperazine. can.

The raw material indolenium salt derivative can be synthesized, for example, by the method described below.

Hydrochloride of phenylhydrazine or 4-chlorophenylhydrazine derivative and 3-methyl-2-butanone are boiled and refluxed in an ethanol solvent under acidic sulfuric acid to produce 2,3,3.
- Synthesize trimethylindolenine derivatives. Next, the derivative and dialkyl sulfate or alkyl halide are combined into 5
A 1-alkyl-2,3,3-trimethylindolenium salt derivative can be synthesized by reacting at 0 to 120°C for 0.5 to 5.0 hours.

In addition, 1-anilino-5-anilinopenta-1,3-diene hydrochloride is a one-tailed form (Bull, In5t).

Phys, Chem, Res, (Tokyo),
13. P511. (1934)).

To create an optical information recording medium using the cyanine dye of the present invention, the cyanine dye is dissolved in the above solvent or mixed solvent, and the solution is applied onto a substrate to form a thin film containing the cyanine dye. . The substrate material may be a commonly used recording material support such as glass, quartz, ceramic, plastic, paper, plate-shaped or foil-shaped metal. Moreover, as a method of application, conventional coating methods such as spraying, roller coating, dipping, and spinning can be used.

〔effect〕

The novel cyanine dye represented by the general formula (1) obtained by the present invention has a maximum wavelength in the near-infrared region and has excellent chemical stability and solubility in various organic solvents.

Therefore, the cyanine dye of the present invention has the advantage that it can be used as a recording and reproducing medium using a laser beam, and also as a sensitizing dye for photoreceptors or photoreceptors for copying and printing, and as a sensitizing dye for silver salt photography. Furthermore, it can be effectively used as a material for optical filters, display materials, paints, etc.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 (1,3,3-trimethyl-5-chloroindo-1'-
Production of ethyl-3r,3t-dimethylindo-2:2'-hebutamethine cyanine perglolate] 2-(6'-acetanilinohexa-1',3',5'- trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate C
H.

was synthesized as follows.

1.2,3.3-tetramethyl-5-chloroindolenium verchlorate 29.6 g, 1-anilino-5-anilinopenta-1,3-diene hydrochloride (melting point 137-1
39'C), 8.2 g of sodium acetate, and 250 cc of acetic anhydride were reacted at 90 to 100°C for 1 hour.

After cooling, the precipitated result was collected by filtration, and the crystals were washed with water and then several times with methanol, chloroform, or acetone. Collection i1
g, 3-island melting point 163-165°C.

2-(6'-acetanilinohexa-1' obtained above)
, 3',5'-trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate 4.6 g
, ■-Ethyl-2.3.3-trimethylindolenium verchlorate (melting point 209-211°C) 2.9g
, sodium acetate 0.82g and n-butanol 50cc
was reacted at 90 to 100°C for 1.5 hours. After cooling, the precipitated crystals were recrystallized several times from methanol. Collection'Bk3
, 4 g, melting point 209-210°C, thick absorption wavelength 748 nm in ethanol.

Example 2 (1,3,3-trimethyl-5-chloroindo-11-
Ethyl-3', 3'-dimethyl-5'-chloroindo-2: Production of 2'-hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa- obtained in Example 1)
1',3',5'-trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate4.
6g, 1-ethyl-2,3,3-trimethyl-5-chloroindolenium ethylsulfonate (wA point 165~
166℃) 3.2g, sodium acetate 0.82g and n-
50 cc of butanol was reacted at 90 to 100°C for 1.5 hours. After cooling, the precipitated crystals were collected by filtration and washed with hot methanol. Yield 3.07g, melting point 225-226℃,
Maximum absorption wavelength in ethanol 7520 m0 Example 3 (1,3,3-trimethyl-5-chloroindo-1'-
Propyl-3', 3'-dimethylindo-2=2'
-Production of hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa1 obtained in Example 1)
/, 3/, 5/ -trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate 4
．． 6g, 1-propyl-2,3,3-trimethylindolenium verchlorate (melting point 164-166°C)3.
02g, sodium acetate 0.82g and lobetanol 5
After cooling, the precipitated crystals were washed with water and then with hot methanol. Yield: 1.98 g, melting point: 175-177°C, maximum absorption wavelength in ethanol: 48 nm Example 4 (1,3,3-trimethyl-5-chloroindo-11-
Production of propyl-3L, 31-dimethyl-5'-chloroindo-2=2'-hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa-obtained in Example 1)
1',3',5'-trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate4.
6 g, 1-propyl-2,3,3-trimethyl-5-chloroindolenium verchlorate (melting point 197-19
9°C), 0.82g of sodium acetate, and 50cc of n-butanol were reacted at 90 to 100°C for 1 hour.

After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed with hot methanol.

Yield: 3.1 g, melting point: 219-221°C, maximum absorption wavelength in ethanol: 754 nm.

Example 5 [1-ethyl-3,3-dimethyl-5-chloroindo-
1'-ethyl-353'-dimethylindo-2:2
Production of '-hebutamethine cyanine verchlorate] One of the raw materials, 2-(6'-acetanilinohexa-1', 3', 5-trienyl)-1-ethyl-
3,3-dimethylindolenium verchlorate was synthesized as follows.

■-Ethyl-2.3.3-Trimethylindolenium barchlorate 8.8g, ■-anilino 5-anilinobenter 1,3-diene hydrochloride 9.1g, sodium acetate 2.6g and anhydrous vinegar A 100cc in 90-100 g. 1 in °C
Allowed time to react. After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed several times with methanol, chloroform, or acetone. Yield: 9.1 g, melting point: 218-219°C.

2-(6'-acetanilinohexa-1' obtained above)
, 3', 5'-trienyl)-1-ethyl-3,
3-dimethyl-5-chloroindolenium verchlorate 4°4g, ■-ethyl-2.3.3-trimethyl-5
- 3.2 g of chloroindolenium ethyl sulfonate,
0.82 g of sodium acetate and 50 cc of n-butanol were reacted at 90 to 100°C for 1.5 hours. After cooling, the crystals were collected by filtration, washed with water, and then washed with hot methanol. Yield 3.2g, melted, lfi 221-222°C, thick absorption wavelength in ethanol 748r+m.

Example 6 [l-ethyl-3,3-dimethylindo-1',3',
3'-trimethylindo-2=2'-hebutamethine cyanine verchlorate and production of II, CI et al.] 2-(6'-acetanilinohexa- obtained in Example 5)
1', 3', 5'-trienyl)-1-ethyl-3
, 3-dimethylindolenium verchlorate 4.4g
, 2.7 g of 1,2゜3.3-tetramethylindolenium verchlorate (melting point 203-204°C), 0.82 g of sodium acetate and 50 cc of n-butanol in 90~
The reaction was carried out at 100°C for 1.5 hours. After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed with hot methanol. Yield 1.9
g, @ point 171-173°C, ultra-thick absorption wavelength 745 nm in ethanol.

Example 7 [1-propyl-3,3-dimethylindo-1'-propyl-3',31-dimethyl-5-chloroindo-2
= Production of 2'-hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa-1', 3', 5'-trienyl)1-propyl-3,3-dimethyl, which is one of the raw materials Indolenium barchlorate C2
H9 was synthesized as follows.

90 ~ 21.1 g of 1-propyl-2,3,3-trimethylindolenium verchlorate, 20.9 g of 1-anilino-5-anilinopenta-1,3-diene hydrochloride, 6.0 g of sodium acetate A, and 1200 cc of anhydrous vinegar N. 110
The reaction was carried out at ℃ for 1.5 hours. After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed several times with methanol, chloroform, or acetone. Yield 11.2g, melting point 212-213℃
.

2-(6'-acetanilinohexa-1' obtained above)
,3',5'-)-lienyl)-1-propyl-3,
4.6 g of 3-dimethyl-5-chloroindolenium verchlorate, 3.4 g of 1-propyl-2,3,3-trimethyl-5-chloroindolenium verchlorate,
0.82 g of sodium acetate and 50 cc of n-butanol were reacted at 90-100°C for 1.5 hours. After cooling, the crystals were collected by filtration, washed with water, and then washed with hot methanol. Yield: 1.7 g, melting point: 176-178°C, maximum absorption wavelength in ethanol: 751 nm.

Example 8 1-propyl-3,3-dimethyl-1'-ethyl-3'
3'-dimethyl-5-chloroindo-2: 2'-heptamethine cyanine verchlorate and production of H7 and 115] 2-(6'-acetanilinohexa- obtained in Example 7)
1'3'5' -trienyl)-1-propyl-3
, 3-dimethylindolenium verchlorate 4.6g
, 3.2 g of 1-ethyl-2,3,3-trimethyl-5-chloroindolenium ethyl sulfonate, 0.82 g of sodium acetate and 50 cc of n-butanol at 90-10 g
The reaction was carried out at 0°C for 1.5 hours. After cooling, the precipitated crystals were collected by filtration.

After washing with water, it was washed with hot methanol. Yield 2.4g, melting point 200-202°C, maximum absorption wavelength in ethanol 75
Qnm.

Next, in order to specifically demonstrate that the cyanine dye of the present invention is excellent as a material for optical information recording media, application examples will be described below.

Application Example 1 The cyanine dye of Example 1 was dissolved in methanol to make a 1% by weight solution. The solution was spin-coated onto an acrylic base plate and dried to obtain a recording layer with a thickness of 450 mm.

A semiconductor laser with a wavelength of 790 nm was used for these recording media, and a beam diameter of 1.54 pm and a linear velocity of 2 m/sec were used.
A signal of 0.7MI+z was recorded at c. When the signal was reproduced by applying a weak laser beam to this recording section, the initial value of C/N was 55 dB. Next, this recording medium was left in an oven at 70° C. for 40 days, and when the signal was reproduced again, the C/N value was 50 dB.

Application Example 2 The cyanine dye of Example 4 was dissolved in 1,2-dichloroethane, and the experiment was carried out in the same manner as in Application Example 1. The initial value of C/N was 56 dB, and the C value after the storage test was 49 dB.

Application Example 3 The cyanine dye of Example 8 was dissolved in methanol, and the experiment was carried out in the same manner as in Application Example 1. The initial value of C is 56dB
The C value after the storage test was 50 dB.

As described above, the cyanine dye of the present invention has significantly superior properties as a material for optical information recording media compared to conventional dyes, and has many industrial advantages.

Claims (1)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 represent hydrogen atoms or chlorine atoms, and R_3 and R_4 represent methyl, ethyl, or propyl groups. In the expression, X^■ represents an acid anion. However, R_
Except when 1 and R_2 are equal and R_3 and R_4 are equal. ) A cyanine dye represented by