JPH06332111A - Silver halide photogrpahic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material sensitive to infrared rays and stable during storage and small in residual dye stains after development processing by incorporating at least one kind of specified dyes. CONSTITUTION:The silver halide photographic sensitive material contains at least one kind of dye represented by the formula in which each of R<1>-R<6> is, independently, alkyl; each of Z<1> and Z<2> is a benzo-condensed ring substituted by a carboxy or sulfo group or a naphtho-condensed ring substituted by a carboxy group; Z<3> is a nonmetallic atomic group necessary to form an N- containing aromatic ring and Z<3> has an acid substituent; (m) is 2 or 3; X is an anion; (n) is 1 or 2, and when the dye forms an intramolecular salt, (n) is 1; and it is preferred that each of Z<1> and Z<2> is a nonmetallic atomic group necessary to form a benzo-condensed ring substituted by carboxy group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, and more specifically, it has absorption in the infrared region and is stable in the photographic material. The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye which is chemically inert and is easily decolorized in the course of photographic processing.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light of a specific wavelength. When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a coloring layer is provided on the side of the photographic photosensitive material farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers as in a multi-layer color light-sensitive material, the filter layer may be located between them. The light scattered during or after passing through the photographic emulsion layer is reflected at the boundary between the emulsion layer and the support or at the surface of the light-sensitive material on the side opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing image blurring, that is, halation, a coloring layer is provided between the photographic emulsion layer and the support or on the surface opposite to the support and the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of a multi-layer color light-sensitive material, an antihalation layer may be placed in the middle of each layer. The photographic emulsion layer is also colored in order to prevent a decrease in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation).

These layers to be colored are often composed of hydrophilic colloids and are therefore usually used for their coloring.
A water-soluble dye is contained in the layer. This dye is required to satisfy the following conditions. (1) It has appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. In other words, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a reduction in sensitivity, latent image regression, or fog. (3) It is not discolored during the photographic processing or is dissolved and removed so that no harmful coloring is left on the photographic light-sensitive material after processing. (4) Excellent stability over time in solution or photographic material.

Many dyes which absorb visible light or ultraviolet rays are known to satisfy such conditions, and for the purpose of improving an image in a conventional photographic element sensitized to a wavelength of 700 nm or less, these dyes are known. Suitable for In particular,
Triarylmethane and oxonol dyes are widely used in this context. On the other hand, development of antihalation and antiirradiation dyes which absorb in the infrared region of the spectrum for recording materials sensitized to infrared wavelengths in recent years, for example, photographic light-sensitive materials as recording materials for recording the output of near infrared laser Is required. For example, one of the exposure methods for such a photographic light-sensitive material is to scan the original image, and the silver halide photographic light-sensitive material is exposed on the basis of the image signal to form a negative or positive image corresponding to the image of the original image. An image forming method using a so-called scanner method for forming is known. In this method, a semiconductor laser is most preferably used as a scanner type recording light source. This semiconductor laser is small, inexpensive, easy to modulate, has a longer life than other He-Ne lasers, argon lasers, etc., and emits light in the infrared region.
The use of a light-sensitive material having photosensitivity in the infrared region has the advantage of improving workability because a bright safelight can be used.

[0005]

However, it has absorption in the infrared region of the spectrum and is suitable for the above conditions (1), (2), (3) and (4), especially the conditions (3) and (4). There are few excellent photosensitive materials that have high photosensitivity in the infrared region and prevent halation and irradiation because there is no such dye, and therefore it is possible to fully utilize the characteristics of the semiconductor laser having excellent performance as described above. The reality is that it cannot be done. To date, many efforts have been made to find dyes satisfying the above conditions, and a large number of dyes have been proposed. For example, indoaniline dyes described in JP-A-50-100116, JP-A-62-123454 and JP-A-62-123454.
3-55544, 64-33547, EP0523.
Tricarbocyanine dyes described in 465A1 and the like,
Oxonol dyes represented by JP-A-1-227148 and merocyanine dyes represented by JP-A-1-234844 are mentioned. In addition, JP-A-2-21614
No. 0 includes tetraaryl type polymethine dyes. However, at present, there are very few dyes that can satisfy all the above conditions.

The objects of the present invention are (1) and (2) described above.
It is to develop a dye satisfying the conditions (3) and (4). In particular, the invention is to provide an infrared-sensitive silver halide photographic light-sensitive material which is stable during storage and has less residual color after development processing.

[0007]

It has been found that the object of the present invention can be achieved by a silver halide photographic light-sensitive material characterized by containing at least one dye represented by the following general formula [I]. . Preferred is a silver halide photographic light-sensitive material having a hydrophilic colloid containing the compound represented by the general formula [I].

[0008]

[Chemical 2]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6, which} may be the same or different, each represents an alkyl group, and Z ¹ and Z ² are benzo substituted with a carboxylic acid group. It represents a non-metal atom group necessary for forming a condensed ring or a benzo condensed ring substituted with a sulfonic acid group (provided that Z ³ contains an acidic substituent) or a naphtho condensed ring substituted with a sulfonic acid group. Z ³ represents a group of non-metal atoms necessary for forming a nitrogen-containing aromatic ring. Here, the nitrogen-containing aromatic ring means an aromatic ring containing only a nitrogen atom as a hetero atom. m is 2 or 3. X represents an anion. n is 1 or 2 and is 1 when the dye forms an intramolecular salt.
Is.

The general formula [I] will be described in detail. R ¹
And R ² may be the same or different and each represents a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, n
-Butyl, n-pentyl, etc.) and may have a substituent such as a sulfonic acid group, a carboxylic acid group or a hydroxyl group. Preferred is an alkyl group having a sulfonic acid group or a carboxylic acid group and having 1 to 5 carbon atoms (for example, 3-sulfopropyl, 4-sulfobutyl, 2-carboxyethyl, etc.).

Z ¹ and Z ² represent a group of non-metal atoms necessary for forming a benzo-condensed ring substituted with a carboxylic acid group, a benzo-condensed ring substituted with a sulfonic acid group or a naphtho-condensed ring substituted with a sulfonic acid group. . However, in the case of a benzo-fused ring substituted with a sulfonic acid group, the nitrogen-containing heterocycle represented by Z ³ contains an acidic substituent. More preferably, it is a group of non-metal atoms necessary for forming a benzo-fused ring substituted with a carboxylic acid group. More preferably, Z ¹
And Z ² are benzo-condensed rings substituted with a carboxylic acid group, and a nitrogen-containing aromatic ring represented by Z ³ is substituted with an acidic substituent.

These fused rings may be substituted with the following substituents. Halogen atom (eg Cl, F, B
r), a substituted amino group (eg, dimethylamino, diethylamino, di (4-sulfobutyl) amino, di (2-carboxyethyl) amino, etc.), a hydroxyl group, or a substituted or divalent linking group. Substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, {eg, methyl group, ethyl group, propyl group, etc. (sulfonic acid, carboxylic acid, hydroxyl group are preferable as the substituent)} and the like Good. The divalent linking group is, for example, -O- or -N.
_{HCO -, - NHSO 2 -,} - NHCO 2 -, - NHC
ONH -, - COO -, - CO -, - SO 2 - and the like are preferable.

The nitrogen-containing aromatic ring represented by Z ³ includes pyrrole, pyrazole, imidazole, triazole, indole, indazole, purine, carbazole and the like. Preferred are pyrrole, pyrazole and imidazole. These heterocycles may be substituted with an alkyl group having 1 to 4 carbon atoms (for example, a methyl group or an ethyl group), a halogen atom (Cl, Br, F), an acidic substituent or the like. A nitrogen-containing aromatic ring (preferably pyrrole, pyrazole, imidazole) substituted with an acidic substituent (particularly preferably a carboxylic acid group) is preferable.

In the present invention, the acidic substituent means a sulfonic acid group or a carboxylic acid group, the sulfonic acid group means a sulfo group or a salt thereof, and the carboxylic acid group means a carboxyl group or a salt thereof. Examples of salts include N
Examples thereof include alkali metal salts such as a and K, ammonium salts, organic ammonium salts such as triethylamine, tributylamine and pyridine.

The anions represented by X include halogen ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonate ion, ethylsulfate ion, PF ₆ ⁻ , BF ₄ ⁻ ,
ClO ₄ ^{− and the} like can be mentioned. Specific examples of the dyes represented by the general formulas [I] and [II] used in the present invention are shown below, but the scope of the present invention is not limited thereto.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

The compounds of the present invention are described in European Patent Publication 0523
465A1 and Journal of Organic Chemistry (J. Org. Chem.) 1992, 57, 4578.
It can be synthesized with reference to -4580.

The dye of the above [I] is preferably dissolved in a suitable solvent [for example, water, alcohol (for example, methanol, ethanol, etc.), methyl cellosolve, etc., or a mixed solvent thereof], or preferably as an aqueous dispersion. It is added to the coating liquid for the photosensitive or non-photosensitive hydrophilic colloid layer. These dyes can be used in combination of two or more kinds. The amount of the above dye used is generally 10 ^{−3.
g / m 2 ~2.5g / m 2} , in particular 10 ^-3 g / m ² ~1.0g /
A preferred amount can be found in the m ² range.

The photographic dye represented by the general formula [I] is particularly effective for the purpose of preventing irradiation, and when it is used for this purpose, it is mainly added to the emulsion layer. The photographic dye of formula [I] is also particularly effective as a dye for preventing halation, and in this case, it is added to the back surface of the support or a layer between the support and the emulsion layer. General formula [I]
The photographic dye can also be advantageously used as a filter dye.

In the present invention, the dye represented by the general formula [I] is preferably used together with the binder. Hydrophilic colloid materials used as binders include gelatin, gelatin substitutes, collodion, gum arabic, alkyl esters of carboxylated cellulose, cellulose ester derivatives such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, 1960 8
There are synthetic resins such as the amphoteric copolymers described in Clavier et al., U.S. Pat. No. 2,949,442, issued Mar. 16, polyvinyl alcohol and other materials well known in the art. Examples of polymeric gelatin substitutes include copolymers of allylamine and methacrylic acid, copolymers of allylamine and acrylic acid and acrylamide, hydrolyzed copolymers of allylamine and methacrylic acid and vinyl acetate, copolymers of allylamine and acrylic acid and styrene, Examples include copolymers of allylamine, methacrylic acid, and acrylonitrile.

Examples of the light-sensitive material of the present invention include a black-and-white photographic light-sensitive material and a color photographic light-sensitive material.

The specific structure of the present invention is described in Japanese Patent Laid-Open No.
No. 226736, photographic processing of the light-sensitive material described in page 5, lower left column, line 12 to page (9), lower left column, line 11;
Descriptions relating to silver halide emulsions, photographic emulsion layers or other hydrophilic colloid layers, etc. can be applied. Less than,
The present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0027]

【Example】

Example 1 1. Preparation of silver halide emulsion 34 g of gelatin was dissolved in 850 ml of H ₂ O, and 1.7 g of sodium chloride, 0.1 g of potassium bromide and the following compound (A) were placed in a container heated at 65 ° C.

[0028]

[Chemical 8]

After adding 70 mg of the above, 500 g of an aqueous solution containing 170 g of silver nitrate, potassium hexachloroiridium (III) so that the molar ratio of iridium to the finished silver halide is 5 × 10 ^-7 , 12 g of sodium chloride and bromide. 500 ml of an aqueous solution containing 98 g of potassium was added by the double jet method to prepare cubic monodispersed silver chlorobromide grains having an average grain size of 0.35 μm. After desalting this emulsion, 50 g of gelatin was added, pH 6.5, pAg
In accordance with 8.1, 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid were added and chemically sensitized at 65 ° C., followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine. 0.2 g of den was added and rapidly solidified (Emulsion A). Next, 0.3 μm cubic monodispersed silver chlorobromide grains were prepared in the same manner as in Emulsion A except that the gelatin solution was heated to 40 ° C., desalted, and then 50 g of gelatin was added to pH 6.
5, pAg8.1. To this emulsion, 2.5 mg of sodium thiosulfate and 5 mg of gold chloride were added and chemically sensitized at 65 ° C., and then 4-hydroxy-6-methyl-1,3,3a, 7.
-Add 0.2 g of tetrazaindene, quench and solidify, Emulsion B
Was adjusted.

2. Preparation of emulsion coating solution Emulsions (A) and (B) were mixed at a weight ratio of 1: 1 and the following additives were added per mol of silver halide to prepare an emulsion coating solution.

(Formulation of Emulsion Coating Solution) a. Spectral sensitizing dye [2] 1.0 × 10 ^-4 mol. Supersensitizer [3] 0.7 × 10 ^-3 mol c. Shelf life improving agent [4] 1 × 10 ⁻³ mol. Polyacrylamide (molecular weight 40,000) 7.5 g e. Dextran 7.5 g f. Trimethylolpropane 1.6 g. Polystyrene sulfonate Na 1.2 g h. Poly (ethyl acrylate / methacrylic acid) latex 12 g i. N, N'-ethylenebis- (vinyl sulfone acetamide) 3.0 g Nu. 1-phenyl-5-mercapto-tetrazole 50 mg

Spectral sensitizing dye [2]

[0033]

[Chemical 9]

Supersensitizer [3]

[0035]

[Chemical 10]

Storability improver [4]

[0037]

[Chemical 11]

3. Preparation of coating solution for surface protection layer of emulsion layer

The container was heated to 40 ° C., and additives were added according to the formulation shown below to prepare a coating liquid.

(Formulation of coating liquid for surface protective layer of emulsion layer)

B. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. N, N'-ethylenebis- (vinyl sulfone acetamide) 2.2 g e. Polymethylmethacrylate fine particles (average particle size 2.0 μm) 2.7 g f. Sodium t-octylphenoxyethoxyethanesulphonate 1.8 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0 g Ji. Sodium polyacrylate 6.0 g Re. C ₈ F ₁₇ SO ₃ K 70 mg Nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70 mg Le. 6 ml of NaOH (1N). Methanol 90 ml Wa. Compound [5] 0.06 g

[0042]

[Chemical 12]

4. Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the formulation shown below to prepare a back layer coating liquid.

(Prescription of Back Layer Coating Liquid) a. Gelatin 100 g b. Dye [A] 4.2 g c. Polystyrene sodium sulfonate 1.2 g d. Poly (ethyl acrylate / methacrylic acid) latex 5 g e. N, N'-ethylenebis- (vinyl sulfone acetamide) 4.8 g f. Compound [5] 0.06 g g. Dye [B] 0.3 g h. Dye [C] 0.05 g Colloidal silica 15 g

Dye [A]

[0046]

[Chemical 13]

Dye [B]

[0048]

[Chemical 14]

Dye [C]

[0050]

[Chemical 15]

5. Preparation of Back Surface Protective Layer Coating Solution A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Back surface protective layer coating liquid formulation)

B. Gelatin 100 g b. Polystyrene sodium sulfonate 0.5 g c. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.9 g d. Polymethylmethacrylate fine particles (average particle size 4.0 μm) 4 g e. Sodium t-octylphenoxyethoxyethanesulphonate 2.0 g f. NaOH (1N) 6 ml. Sodium polyacrylate 2.4 g h. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0 g Li. C ₈ F ₁₇ SO ₃ K 70 mg Nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70 mg Le. 150 ml of methanol. Compound [5] 0.06 g

6. Creating photographic material

The above-mentioned back layer coating solution was coated together with the back layer surface protective layer coating solution on the side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3 g / m ² . Following this, the emulsion coating liquid and the surface protective layer coating liquid described above were applied to the opposite side of the support, and the coating Ag amount was 2.3 g / m ^2.
And the coating amount of gelatin in the surface protective layer was 1 g / m ² (photographic material 1).

Further, instead of the dye [A], the comparative dyes [D], [E] and [F] and the dye (1) of the present invention,
(2), (4), (7), (12), (13), (17),
Photographic materials 2 to 2
11 was created. Dyes [A] and [F] are disclosed in
No. 171136, and the dyes [D] and [E] are those described in European Patent Publication No. 523465A1.

[0056]

[Chemical 16]

7. Evaluation of Storage Stability The photosensitive materials shown in Table 1 prepared by the above method were treated with a humidity of 70
%, The reflectance spectrum was measured after standing at 50 ° C. for 5 days, and the change rate of the light absorption rate at the absorption maximum wavelength of each dye (absorption rate after standing at 50 ° C., 70% RH / 50 ° C., 70%
The absorptivity before standing in% RH) was calculated and shown in Table 1.

8. Evaluation of Decoloring Property The light-sensitive materials shown in Table 1 were subjected to the following image forming treatment, and the reflection spectrum of a white background portion was measured. The residual color ratio of the dye was calculated by comparing the maximum light absorption of the dye before and after the image forming process, and the results are shown in Table 1.

The photographic materials 1 to 9 were kept at a temperature and humidity of 25 ° C. and 60%, left for 7 days after coating, and subjected to scanning exposure for 10 ⁻⁷ seconds using a semiconductor laser of 830 nm at room temperature, and a roller-conveying type automatic developing machine. By using the following developer [I],
Development processing was performed with the fixing solution [I]. The developing time is 7 seconds, the fixing is 7 seconds, the water washing is 4 seconds, and the draining and drying are 11 seconds. At this time, the transport speed was 3000 mm / min.

Composition of developer [I]

Potassium hydroxide 29 g Sodium sulfite 31 g Potassium sulfite 44 g Ethylenetriaminetetraacetic acid 1.7 g Boric acid 1 g Hydroquinone 30 g Diethylene glycol 29 g 1-Phenyl-3-pyrazolidone 1.5 g Glutaraldehyde 4.9 g 5-Methylbenzotriazole 60 mg 5-nitroindazole 0.25 g potassium bromide 7.9 g acetic acid 18 g upto 1000 ml pH 10.3 Fixer [I] composition

Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 20 mg Sodium hydroxide 7 g Aluminum sulfate 10 g Boric acid 10 g Sulfuric acid 3.9 g Acetic acid 15 g H ₂ O upto 1000 ml pH 4.30 The results obtained are shown in Table 1.

[0063]

[Table 1]

From the results shown in Table 1, it is clear that the dye of the present invention is effective in stability and residual color.

[0065]

The light-sensitive material of the present invention is excellent in storage stability and, at the same time, has little residual color after image forming processing.

[Procedure amendment]

[Submission date] July 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

[0017]

[Chemical 4]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

[0037]

[Chemical 11]

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one dye represented by the following general formula [I]. [Chemical 1] In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6, which} may be the same or different, each represents an alkyl group, and Z ¹
And Z ² form a benzo-condensed ring substituted with a carboxylic acid group, a benzo-condensed ring substituted with a sulfonic acid group (provided that Z ³ includes an acidic substituent), or a naphtho-condensed ring substituted with a sulfonic acid group. Represents a group of non-metal atoms required for. Z ³ represents a group of non-metal atoms necessary for forming a nitrogen-containing aromatic ring. m is 2 or 3. X represents an anion. n is 1 or 2, and is 1 when the dye forms an intramolecular salt. 2. In the dye represented by the general formula [I], Z
^{2. The} silver halide photographic light-sensitive material according to claim ^{1, wherein 1} and Z ² are a group of non-metal atoms necessary for forming a benzo-fused ring substituted with a carboxylic acid group. 3. In the dye represented by the general formula [I], Z
^{3. The} silver halide photographic light-sensitive material according to claim 2, wherein 3 is a group of non-metal atoms necessary for forming a nitrogen-containing aromatic ring substituted with an acidic substituent.