JPH08245902A - Dispersion of fine solid particle of cyanine compound - Google Patents

Abstract

PURPOSE: To provide a dispersion of fine solid particles of a cyanine compound having a specific chemical structure having absorptivity in a region of wavelength longer than the maximum absorption wavelength determined in a solution by at least a prescribed wavelength, resistant to dissolution, having excellent again stability and useful for (photographic) dye, ink, etc. CONSTITUTION: This dispersion of fine solid particles is composed of a cyanine compound having absorptivity in a region of wavelength longer than the maximum absorption wavelength determined in a solution by >=50nm and expressed by formula I [Z<1> and Z<2> are each a non-metallic atom group necessary for forming a (condensed) 5- or 6-membered nitrogen-containing heterocyclic group; R<1> and R<2> are each an alkyl, an alkenyl or an aralkyl; R<3> and R<5> are each H or together form a ring; R<4> is H, a halogen, an alkyl, an aryl, etc.; (a) and (b) are each 0 or 1; X<1> is an anion; the molecule is free from an acidic substitutent], e.g. the compound of formula II. The average particle diameter of the dispersed particles is preferably 0.01-0.1μm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solid fine particle dispersion of a tricarbocyanine compound. The present invention can be used as a dye, a photographic dye, a filter dye, an ink, a recording compound for an optical information recording medium, a stain for a biological sample such as cells, a medicine, or an intermediate thereof.

[0002]

2. Description of the Related Art In recent years, for the purpose of easily handling a light-sensitive material in a bright room, a light-sensitive material such as a photo-taking device or an automatic developing machine is conveyed to identify the presence or absence of the light-sensitive material. An optical sensor is used in the system. In particular, many of these devices for black and white photosensitive materials such as X-ray
A light emitting diode or a semiconductor laser that emits light with a wavelength of 700 nm or more is used as a light source, and a light receiving element having a light receiving sensitivity peak near 900 nm and a sensitivity range of about 700 nm to 1200 nm is used in combination. Therefore, for detection by transmitted light, the photosensitive material must have at least 700
It was desired to have a light absorption property of nm or more. on the other hand,
Photosensitive materials (especially black-and-white photosensitive materials such as X-rays) have high needs for rapid processing. In addition, there is an increasing need for reducing the replenishment of processing liquid. For this reason, there is a large tendency to decrease the coated silver amount. However, at this time, since the amount of coated silver was reduced, the light-shielding property of the infrared sensor installed in the transport system such as the photographing device and the automatic developing machine was reduced, and the position of the photosensitive material could not be detected, resulting in poor transport. Will cause

For this sensor detection, a technique of dyeing a photosensitive material with a dye has been proposed. The dye for sensor detection needs to satisfy the following conditions. (1) It has proper spectral absorption according to the infrared sensor. (2) Photochemically inert. That is, the performance of the silver halide photographic emulsion should not be adversely affected by sensitivity, latent image regression or fog. (3) Do not leave harmful coloring on the photographic light-sensitive material after processing. (4) Excellent stability over time in a solution or a photographic light-sensitive material. (5) The burden on the processing liquid is small.

As such a dye, for example, JP-A-3
No. 138640 discloses a solid fine particle dispersion of an indotricarbocyanine dye, but it is not suitable for reducing the replenishment of the processing liquid because it has a heavy load on the processing liquid because of its elution property.

[0005]

Therefore, the object of the present invention is to satisfy the above-mentioned conditions. 1) The absorption in the visible region is small and the absorption region is in the long wave region. 2) It is non-eluting.
3) Excellent stability over time. It is to provide a solid fine particle dispersion having features such as the above.

[0006]

The object of the present invention can be achieved by a solid fine particle dispersion of a cyanine compound represented by the following general formula (I) having a wavelength longer than 50 nm from the maximum absorption wavelength when measured in a solution.

[0007]

[Chemical 4]

In the formula, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may be condensed, and R ¹ and R ² are each an alkyl group. , An alkenyl group or an aralkyl group, R ³ and R ⁵ each represent a hydrogen atom or an atomic group necessary for forming a 5- or 6-membered ring by connecting with each other, and R ⁴ represents a hydrogen atom, a halogen atom or an alkyl group. , An aryl group, NR ⁶ R ⁷ , SR ⁸ or OR ⁹ , R ⁶ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents an alkyl group or an aryl group, and R ⁶ and R ⁷ are linked to each other. You may. R ⁸ and R
⁹ represents an alkyl group or an aryl group. However, when R ⁴ is a hydrogen atom, R ³ and R ⁵ are connected to each other. a and b each represent 0 or 1, and X ¹ represents an anion. However, the molecule does not contain an acidic substituent. The general formula (I) will be described in detail. The optionally condensed 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ¹ and Z ² is an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, a thiazole ring, a benzothiazole ring, or a naphthothiazole. Examples thereof include a ring, an indolenine ring, a benzoindolenine ring, an imidazole ring, a benzimidazole ring, a naphthimidazole ring, a quinoline ring, a pyridine ring, a pyrrolopyridine ring and a furopyrrole ring. A 5-membered nitrogen-containing heterocycle in which a benzene ring or a naphthalene ring is condensed is preferable, and an indolenine ring is most preferable.
These rings may be substituted. As a substituent,
Lower alkyl group (eg methyl, ethyl), alkoxy group (eg methoxy, ethoxy), phenoxy group (eg unsubstituted phenoxy, p-chlorophenoxy), halogen atom (Cl, Br, F), alkoxycarbonyl group (For example, ethoxycarbonyl), a cyano group, a nitro group and the like can be mentioned. More preferred is an indolenine ring which is unsubstituted or substituted with a chlorine atom, a methoxy group or a methyl group.

The alkyl group represented by R ¹ , R ² , R ⁴ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (eg, methyl group). , Ethyl, propyl, butyl, isobutyl, pentyl, hexyl). Further, it may be substituted with a hydroxy group, a halogen atom (F, Cl, Br) or an alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl) and the like. The aralkyl group represented by R ¹ and R ² is preferably an aralkyl group having a carbon number of 7 to 12 (eg, benzyl, phenylethyl), and the aryl moiety has a substituent (eg, methyl, alkoxy, chloro atom). You may have. The alkenyl group represented by R ¹ and R ² is preferably an alkenyl group having a carbon number of 2 to 6, and examples thereof include a 2-pentenyl group, a vinyl group, an allyl group, a 2-butenyl group, and a 1-propenyl group. be able to. R ³ and R ⁵ may be linked to each other to form a 5- or 6-membered ring (eg, cyclopentene, cyclohexene), and may have a substituent (eg, methyl, t-butyl, phenyl).

R^FourThe halogen atom represented by F, C
1 and Br. R^Four, R⁶, R⁷, R⁸And R
⁹The aryl group represented by has a carbon number of 6 to 15
Preferred is a phenyl group or a naphthyl group.
The aryl group may be substituted, and as the substituent,
Z¹The substituents described in the above can be mentioned. R⁶And R
⁷May combine with each other to form a heterocycle. Hete
Examples of the ring include piperidine, morpholine, piperazine, etc.
Substituents (eg methyl, phenyl
Group, ethoxycarbonyl, etc.). X¹
The anion represented by is a halogen ion (Cl,
Br, I), p-toluenesulfonate ion, ethyl sulphate
Acid ion, PF₆ ^-, BF_Four ^-, ClO_Four ^-Etc.
Be done.

More preferably, R ¹ and R ² are unsubstituted alkyl groups, R ³ and R ⁵ are linked to form a 5- or 6-membered ring, and R ⁴ is NR ⁶ R ⁷ . Particularly preferably,
At least one of R ⁶ or R ⁷ is a phenyl group,
More preferably, R ⁶ and R ⁷ are phenyl groups.
In the present invention, the acidic substituent represents a water-soluble group such as a sulfonic acid group, a carboxylic acid group and a phosphonic acid group. Here, the sulfonic acid group means a sulfo group and a salt thereof, the carboxylic acid group means a carboxyl group and a salt thereof, and the phosphonic acid group means a phosphono group and a salt thereof. Examples of salts include alkali metal salts such as Na and K, ammonium salts, organic ammonium salts such as triethylammonium, tributylammonium, pyridinium and tetrabutylammonium.

In the present invention, more preferably, a solid fine particle dispersion of a cyanine compound represented by the following general formula (II), whose spectrum in the solid state is 50 nm or more longer than the maximum absorption wavelength when measured in a solution, is there.

[0013]

Embedded image

Where Z³And Z^FourIs benzo-naphtho condensation
Represents an atom necessary for forming a ring, R^TenAnd R¹¹Are each
Represents an alkyl group, an aralkyl group or an alkenyl group,
R¹²And R¹⁴Are each a hydrogen atom or 5 connected to each other.
Or represents a group of atoms necessary for forming a 6-membered ring, R¹³Is water
Elementary atom, alkyl group, aryl group, NR¹⁹R²⁰, SR ^{twenty one}
Or OR^{twenty two}Represents R¹⁹Is a hydrogen atom, an alkyl group or
Represents an aryl group, R²⁰Is an alkyl group or aryl
Represents a group, R¹⁹And R²⁰Are linked together to form a ring
Good. R^{twenty one}And R^{twenty two}Are each an alkyl group or an aryl group
Represents R^Fifteen, R¹⁶, R¹⁷And R¹⁸Are each an alkyl group
Represent, R^FifteenAnd R¹⁶And R¹⁷And R¹⁸Combine to form a ring
May be. X²Represents an anion. However, acidic in the molecule
Contains no substituents.

The general formula (II) will be described in detail. Z³as well as
Z^FourA benzo- or naphtho-condensed ring formed by¹Over
And Z³It may be substituted with the substituent described in. R^Ten,
R¹¹, R¹³, R^Fifteen, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R
^{twenty one}And R^{twenty two}The alkyl group represented by is described in the general formula (I).
Solid R¹And R²Is synonymous with the alkyl group in. R
^FifteenAnd R¹⁶And R¹⁷And R¹⁸Are connected to each other to form a ring (eg
Cyclohexane, etc.) may also be formed. R^TenAnd R¹¹so
The alkenyl group and aralkyl group represented are each represented by R¹And R
²And the alkenyl group and the aralkyl group.
R¹³, R¹⁹, R²⁰, R^{twenty one}And R^{twenty two}An aryl group represented by
Is R in the general formula (I) ^FourAnd the like are synonymous with the aryl group.
R¹³The halogen atom of is R^FourSynonymous with the halogen atom of
It R¹²And R¹⁴Ring formation by R³And R^Fiveby
Synonymous with ring formation. R¹⁹And R²⁰Ring formation by R
⁶And R⁷It is synonymous with the ring formation of. X²Is the general formula (I)
X¹Is synonymous with. Preferably Z³And Z^FourBen
Forming a zo-fused ring, R^TenAnd R¹¹Is an unsubstituted alkyl group
And R¹²And R¹⁴Combine to form a 5- or 6-membered ring
Then R^Fifteen, R¹⁶, R¹⁷And R¹⁸Is a methyl group, and R¹³
Is NR¹⁹R²⁰Is a compound represented by. Particularly preferred
Is R¹⁹Or R²⁰Have a phenyl group on at least one of
And more preferably R¹⁹And R²⁰But
It is a phenyl group.

In the present invention, more preferred is a solid fine particle dispersion of a cyanine compound represented by the general formula (III), which has a long wavelength of 50 nm or more from the maximum absorption wavelength when measured in a solution.

[0017]

[Chemical 6]

Where Z^FiveAnd Z⁶Are benzo or
Represents an atom necessary to form a naphtho-condensed ring, R²⁰as well as
R^{twenty one}Is an alkyl group, an aralkyl group or an alkenyl, respectively.
Represents a group, R^{twenty three}And R^{twenty four}Are each an alkyl group or aryl
Represents a radical, R^{twenty five}, R²⁶, R ²⁷And R²⁸Are each alkyl
Represents a group, R^{twenty five}And R²⁶And R²⁷And R²⁸Form a ring by connecting
May be done. X³Represents an anion. However, in the molecule
Does not contain acidic substituents.

The general formula (III) will be described in detail. The benzo- or naphtho-condensed ring formed by Z ⁵ and Z ⁶ may be substituted with the substituent described for Z ^{1 and the} like. R ²⁰ , R ²¹ ,
The alkyl group represented by R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²³ and R ²⁴ has the same meaning as the alkyl group of R ¹ and R ² in formula (I). R ²⁵ and R ²⁶ and R ²⁷ and R ²⁸ may combine with each other to form a ring (eg, cyclohexane).
The alkenyl group and aralkyl group represented by R ²⁰ and R ²¹ have the same meaning as the alkenyl group and aralkyl group of R ¹ and R ² . The aryl group represented by R ²³ and R ²⁴ has the same meaning as the aryl group represented by R ^{4 in} formula (I). X ³ has the same meaning as X ^{1 in} formula (I). More preferably, Z ⁵
And Z ⁶ form a benz fused ring, R ²⁰ and R ²¹ are unsubstituted alkyl groups, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are methyl groups, and R ²³ and R ²⁴ are phenyl groups. Is. Specific examples of the present invention are shown below, but the scope of the present invention is not limited thereto.

[0020]

[Chemical 7]

[0021]

Embedded image

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

The maximum absorption wavelength (λmax) of the compound of the present invention in a solution can be obtained by measuring an absorption spectrum using a solvent as a solution of about 6 × 10 ^-6 mol / liter. The maximum absorption wavelength range is preferably about 600 to 850 nm, 75
0 to 850 nm is particularly preferred. The maximum absorption wavelength of the solid fine particle dispersion was coated with gelatin on a polyester terephthalate film at 25 mg / m ² , and the maximum absorption wavelength was determined by measuring the spectral absorption with a spectrophotometer. To prepare a solid fine particle dispersion, a dispersing machine such as a ball mill, a vibration ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill or a roller mill described in JP-A No. 52-92716 and WO 88/074794 is used. However, a vertical or horizontal medium disperser is preferable. In either case, a solvent (for example, water, alcohol, etc.) may coexist, and it is preferable to use a dispersing surfactant. As the dispersing surfactant, the anionic surfactants described in JP-A No. 52-92716 and WO88 / 04794 are mainly used. In addition, an anionic polymer and a nonionic or cationic surfactant can be used if necessary. Preferably, it is an anionic surfactant. Alternatively, the compound of the present invention may be dissolved in a suitable solvent, and then a poor solvent for the compound of the present invention may be added to obtain a fine particle dispersion. Also in this case, the above-mentioned dispersing surfactant may be used.

The finely divided particles of the compound of the present invention in the dispersion have an average particle size of 0.005 to 10 μm, preferably 0.0
It is preferably 1 to 1 μm, more preferably 0.01 to 0.5 μm, and in some cases 0.01 to 0.1 μm. The solid fine particle dispersion of the compound of the present invention can be used by the method described in Japanese Patent Application No. 6-227983. It is also useful as a photographic dye (anti-irradiation, anti-halation, filter dye). In that case, the methods described in JP-A-62-121354 and JP-A-3-13937 can be used. Furthermore, the solid dispersion of the dye of the present invention can be used as a dye for dyeing, an ink, a dye for a filter, a recording compound for an optical information recording medium, a stain for biological samples such as cells, or a pharmaceutical.

[0027]

EXAMPLES Examples of solid fine particle dispersions of these compounds will be shown below. Example 1 (Synthesis of Compound 2) 1, 2, 3, 3-tetramethyl-5
-Chloroindolenium-p-toluenesulfonate 11.4 g, N- (2,5-dianilinomethylene cyclopentylidene) -diphenylaminium perchlorate 7.2 g, ethyl alcohol 100 ml, acetic anhydride 6
ml and triethylamine 12 ml were stirred at an external temperature of 100 ° C. for 1 hour, and the precipitated crystals were separated by filtration. The crystals were washed with 100 ml of methyl alcohol and further with 300 ml of water. The crystals obtained corresponded to a dry solids content of 7.3 g. Melting point: 250 ° C. or higher, λmax: 800.8 nm, ε:
2.14 × 10 ⁵ (chloroform)

(Solid Fine Particle Dispersion of Compound 2) The compound was treated as a wet cake without drying as much as possible, and 15 g of a 5% carboxymethylcellulose aqueous solution was added to 2.5 g of the dried solid content to make a total amount of 63.3.
It was mixed well as g to make a slurry. Diameter 0.8-1.
Prepare 100 mm of 2 mm glass beads, put this slurry in a disperser (1 / 16G sand grinder mill; manufactured by AIMEX Co., Ltd.) and disperse for 12 hours, and then add water so that the dye concentration becomes 2%. A dye dispersion was obtained.

(Preparation of coating film) A polyester terephthalate film coated with an undercoat was coated in the following coating amount. -Gelatin 3 g / m ² -Compound 2 solid fine particle dispersion 25 mg / m ² -For the hardener, 1,2-bis (sulphoracetamido) ethane was applied at 56 mg / m ² per side.・ Compound A 20 mg / m ²

[0030]

[Chemical 12]

(Measurement of Spectral Absorption) The obtained coating film was measured for spectral absorption with a spectrophotometer (U-2000: manufactured by Hitachi Ltd.) to obtain a maximum absorption wavelength (λmax) value. It was found that the film absorption spectrum obtained by this method had a λmax of 910 nm and showed little absorption in the visible region, and was suitable for use as a dye for detecting a sensor in a light-sensitive material. Further, it was found that the solid dispersion of the dye of the present invention remained unchanged in the film by the development treatment and was suitable for the purpose of reducing the replenishment of the treatment liquid. Further, it was found that the absorption was stable without change even after aging at high temperature. Example 2 By the same operation as in Example 1, the following dye and its solid dispersion were obtained. Λmax and λma of film absorption in solution of dye
x is shown in Tables 1-4. All had the same effects as in Example 1.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

Claims (3)

[Claims] 1. A solid fine particle dispersion of a cyanine compound represented by the following general formula (I), which has a long wavelength of 50 nm or more from the maximum absorption wavelength when measured in a solution. Embedded image In the formula, Z ¹ and Z ² each represent a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may be condensed, and R ¹ and R ² are each an alkyl group or an alkenyl group. Or an aralkyl group, R ³ and R ⁵ each represent a hydrogen atom or an atomic group necessary for connecting with each other to form a 5- or 6-membered ring, and R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. , NR ⁶ R ⁷ , SR ⁸ or OR ⁹ , R ⁶ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents an alkyl group or an aryl group, R ⁶
And R ⁷ may be linked to each other. R ⁸ and R ⁹ represent an alkyl group or an aryl group. However, when R ⁴ is a hydrogen atom, R ³ and R ⁵ are linked to each other. a and b each represent 0 or 1, and X ¹ represents an anion. However, the molecule does not contain an acidic substituent. 2. A solid fine particle dispersion of a cyanine compound represented by the following general formula (II), which has a long wavelength of 50 nm or more from the maximum absorption wavelength when measured in a solution. Embedded image In the formula, Z ³ and Z ⁴ each represent an atom necessary for forming a benzo or naphtho condensed ring, R ¹⁰ and R ¹¹ each represent an alkyl group, an aralkyl group or an alkenyl group, and R ¹²
And R ¹⁴ each represent a hydrogen atom or an atomic group necessary for connecting to each other to form a 5- or 6-membered ring, and R ¹³ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, NR ¹⁹ R
²⁰ , R ²¹ or OR ²² , R ¹⁹ represents a hydrogen atom, an alkyl group or an aryl group, R ²⁰ represents an alkyl group or an aryl group, and R ¹⁹ and R ²⁰ may be linked to each other. R ²¹ and R ²² represent an alkyl group or an aryl group, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each represent an alkyl group, and R ¹⁵ and R ¹⁶ and R ¹⁷ and R ¹⁸ are linked to form a ring. You may. X ² represents an anion. However, the molecule does not contain an acidic substituent. 3. The maximum absorption wavelength when measured in solution
Represented by the following general formula (III), which is a long wave of 50 nm or more
Solid fine particle dispersion of a cyanine compound. [Chemical 3]Where Z^FiveAnd Z⁶Are each a benzo or naphtho fused ring
Represents an atom necessary to form²⁰And R^{twenty one}Are each
R represents an alkyl group, an aralkyl group or an alkenyl group, and R
^{twenty three}And R^{twenty four}Each represents an alkyl group or an aryl group,
R^{twenty five}, R²⁶, R ²⁷And R²⁸Each represents an alkyl group, R
^{twenty five}And R²⁶And R²⁷And R²⁸May combine to form a ring
Yes. X³Represents an anion. However, acidic substituents in the molecule
Does not include.