JPH02165133A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve image quality without impairing sensitivity and to reduce occurrence of residual color after development processing by incorporating a specified dye in a hydrophilic colloidal layer. CONSTITUTION:The hydrophilie colloidal layer contains at least one of the dyes represented by formula 1 in which each of X and Y is cyano, carbamoly, carboxy, or carboxylate; each of R1 and R2 is an optional substituent; each of R3 and R4 is H, alkyl, aryl, or a heterocyclic group, and each may form a ring together with each other; m is an integer of 0 - 6; and n is an integer of 0 - 4, thus permitting the obtained photosensitive material to have superior absorption spectral characteristics and to contain a dye decolorizalbe by development processing and small in color staining due to the residual dye effluent from the photosensitive material after the development processing, and inactive to the photographic emulsion.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material containing a dye, and particularly to a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. Related to silver photographic materials.

[Background of the invention]

Silver halide photographic materials (hereinafter referred to as "photosensitive materials") contain dyes for the purpose of absorbing light of specific wavelengths to prevent filter halation, prevent irradiation, or adjust the sensitivity of photographic emulsions. It is well known that hydrophilic colloid layers are colored with dyes.

A filter layer is usually located above a photosensitive emulsion layer or between two emulsion layers, and serves to convert incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, in order to improve the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back of the support to prevent harmful effects such as at the interface between the emulsion layer and the support or on the back of the support. It is often done to prevent halation by absorbing reflected light, or to prevent irradiation by coloring the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains, etc. ing.

Dyes used for such purposes have good absorption spectral properties depending on the intended use, and are completely decolorized during the photographic processing process, making them completely blind. Easily eluted from photographic materials,
There should be no residual color staining caused by the dye after the development process, there should be no adverse effects such as fogging or desensitization on the photographic emulsion, there should be no diffusion from the dyed layer to other layers, and there should be no residual color contamination caused by dyes in the solution or photographic materials. It must satisfy various conditions such as excellent stability over time and no discoloration.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, British Patent No. 506°385, U.S. Patent No. 3,247,127, Japanese Patent Publication No. 39-22069,
oxonol dyes described in U.S. Pat. No. 43-13168, styryl dyes as typified by U.S. Pat. No. 1,845,404, merocyanine dyes as typified by U.S. Pat. No. 2,493,747, and U.S. Pat. No. 2,843.486. There are cyanine dyes represented by No. However, the reality is that there are very few good dyes that satisfy all of the above conditions17 and can be used in photographic materials, especially dyes that absorb in the red to infrared region and that meet the above conditions. Very few dyes were known that were satisfactory.

- On the other hand, in recent years, recording materials sensitized to infrared wavelengths, such as antihalation and irradiation absorbing in the infrared region of the spectrum, have been developed for use in photographic materials such as recording materials that record the output of near-infrared lasers. [Objective of the Invention] Therefore, the object of the present invention is to develop a dye that has good absorption spectrum characteristics in the red to infrared region, is decolorized during photographic processing, and is suitable for use in photographic materials. It is an object of the present invention to provide a silver halide photographic light-sensitive material containing a dye that is eluted from the inside and causes very little residual color staining after processing and is inert to photographic emulsions.

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide photographic material having a hydrophilic colloid layer containing at least one dye represented by the following general formula CI).

General formula (I) In the formula, X and Y each represent a cyano group, a carbamoyl group, a carboxyl group, or a carboxylic acid ester group, R6 and R2 each represent a substitutable group, and R3 and R4 each represent hydrogen. It represents an atom, an alkyl group, an aryl group, or a heterocyclic group, and R3 and R1 may form a ring. Vinegar is 0-6
It represents an integer of 0-4.

The present invention will be explained in more detail below.

Among the groups represented by , hydroxyethyl/carbonyl, and the like.

Examples of substitutable groups represented by R1 and R1 include halogen atoms, alkyl, aryl, heterocycle, aralkyl, alkoxy, aryloxy, hydroxy,
Acyloxy, carboxy, alkylsulfonyl, aryloxycarbonyl, mercapto, alkylthiokylsulfonyl, arylsulfonyl, acyl, acylamino, sulfonemide, carbamoylsulfamoyl, sulfo or its salt, cyanide, nide[], isocyanate, ureido, etc. Each group is mentioned. When m and n are each 2 or more, a plurality of l(.

and R may be the same or different.

Examples of the alkyl group represented by R and R4 include methyl, ethyl, propyl, cyclohexyl, benzyl, phenethyl, etc., and examples of the aryl group include phenyl, naphthyl, and heterocyclic groups. Examples of groups 1 and 1 include pyridyl, tetrahydrofuryl, and sulfolanyl.

These groups may have a substituent, for example, a halogen atom or a polygroup such as hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, alkylsulfonyl, sulfonamide, cyano, sulfo, acylamino, carbamoyl, or sulfamoyl. can be mentioned.

Furthermore, R3 and R4 may be combined to form a ring (for example, a morpholine ring).

At least one of R, R, R, and R4 may itself be a water-soluble group such as a sulfo group or a carboxyl group, or a group having a sulfo group or a carboxyl group as a substituent. preferable.

The dye represented by the general formula (i) used in the present invention (
Specific examples of dyes (hereinafter referred to as dyes of the present invention) are shown below.
The present invention is not limited to these.

(lO) SO,K SO, to Next, a method for synthesizing the compound of the present invention will be described.

The compound of the present invention can be easily obtained by the following steps.

(R1)ffi Regarding this synthesis method, see, for example, Chemistry Letters, 1987.
No. 9, P1761-1762 can also be considered.

Alternatively, in the above reaction, instead of the N,N-dialkyl-P phenylenediamine compound, 4-nitrone-N,
It can also be obtained by reacting N-dialkylarylamine.

In the light-sensitive material of the present invention, the dye represented by the general formula 1 can be incorporated into a silver halide emulsion and used as an irradiation-preventing dye, or it can be used as an irradiation-preventing dye in a non-photosensitive hydrophilic colloid layer. It can be used as a filter dye or an antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes.

Incorporation of the dye of the present invention into a silver halide emulsion layer or other hydrophilic colloid layer can be easily carried out by a conventional method.

Generally, a dye or an organic or inorganic alkali salt of the dye is dissolved in water, an aqueous dye solution of an appropriate concentration is added to a coating solution, and coating is carried out by a known method to incorporate the dye into the photosensitive material. be able to. The content of these dyes varies depending on the purpose of use, but is generally applied in an amount of 1 to 800 a+g per 11 areas of the photographic material.

The light-sensitive materials to which the present invention is applied include not only black-and-white photographic materials but also color photographic materials. 1
Examples of the 19 materials include photosensitive materials for printing. The silver halide used in the present invention may be, for example, silver chloride, silver bromide, silver iodide, silver chloride, silver chloroiodide, silver iodobromide, or silver chloroiodide. .

Silver halide grains in photographic emulsions may be so-called regular grains, which have regular crystal structures such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as spherical shapes. , one with crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method.
(RD), Volume 176, No. 17643 (December 1978).

The method described in p. 22-23, No. 18716 (November 1978), p. 648 can be followed.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allylthiocarbamide, thiourea, thiosulfate, thioether and cystine; botanium chloroaurate;
Examples include noble metal sensitizers such as aura thiosulfate and potassium chloroparadate; reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. The spectral sensitizing dye used is Research Disclosure (cited above) No. 17643. Those described in Section (2) can be used.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of capri during the manufacturing process, storage or processing of the light-sensitive material.

These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene, l-722-5-mercaptotetrazole, and many other heterocyclic compounds. A large number of compounds such as mercury compounds, mercapto compounds, and metal salts have been known for a long time.

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used.

In addition to the above-mentioned materials, the light-sensitive material of the present invention includes a desensitizer, a brightener, a coupler, a hardening agent, a coating aid, a plasticizer, a slippery agent, a matting agent, a high tailing point organic solvent, a stabilizer, and a developer. Accelerators, antistatic agents, anti-stain agents, etc. can be used.

Regarding these additives, see Research Disclosure (supra) No. 17643. Those described in sections I to XvI can be used.

Any known method can be used for the photographic processing of the light-sensitive material of the present invention, and known processing solutions can be used. Also, the processing temperature is usually 18°C to 50°C.
temperature chosen between 18 °C or below 50 °C
The temperature may exceed °C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

〔Effect of the invention〕

The silver halide photographic material of the present invention has good image quality, does not impair sensitivity, and has little residual color after development.

In addition, the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is colored with a water-soluble dye, so it does not adversely affect the photographic properties of the photographic emulsion, has good stability due to preservation, and can be easily processed by photographic processing. It is extremely superior in that it can be easily decolored.

〔Example〕

EXAMPLES Next, the present invention will be described in more detail with examples, but the present invention is not limited thereto.

Example 1 3.59 g of gelatin was added and dissolved in 35 mQ of distilled water, and 2.5 g of exemplified dyes (1), (2) and (3) of the present invention were added thereto, respectively. Add 5 m12 of an aqueous solution containing 10-' moles of OX, and then add 1-25 m of an aqueous solution of 10% saponin + if
1 and 0.75 ml of 1% formalin solution were added, and water was added to bring the total volume to 50 ml. This dye solution was coated onto an acetylcellulose film support and dried to give samples 1.2 and 3. Comparative samples 4 and 5 were also prepared in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention.

Comparative dye (A) Comparative dye (B) Each of these samples was immersed in a developer having the following composition at 25° C. for 1 minute, washed with water for 20 seconds, and then dried.

(Composition of developer) Meter
3.0g Sodium sulfite (anhydrous) 45.09 Hydroquinone 12.09 Sodium carbonate (
I water salt) 80.1) Potassium 9 bromide
Add 2.0g water to make 1Q.

The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below.

(El is the absorbance before immersion in the developer, and E is the absorbance after immersion in the developer.) As is clear from Table 1, the dye of the present invention is superior to the comparative dyes. It was found that it exhibits decolorizing properties.

Example 2 80 mol% silver chloride, 19.5 mol% silver bromide and 0 silver iodide
．． A silver chloroiodobromide gelatin emulsion consisting of 5 mol % and having an average grain size of 0.32 μm was prepared. This gelatin emulsion contains 489 kg of silver and 75 g of gelatin. ) per 2.4-dichloro-6-hydrogycy 1.3.5-1
-Riazine sodium salt (1% aqueous solution) 35+aQ and sabot,? After adding 50 m (2) of a 10% aqueous solution, it was coated on a subbed-treated poly-1-ethylene terephthalate film support so that 50 m9 of silver was contained per 100 cm2, and dried.

Further, on this emulsion layer, a protective layer containing the exemplary dye (4) of the present invention and having the composition shown below was coated to a dry film thickness of about 2 microns. (Sample 6) (Protective layer composition) Gelatin 409 water

85ollQ Exemplary dye of the present invention (4) (2% aqueous solution) 100m42
2.4-dichloro-6-hydrocoir 1.3.5- ) riazine sodium salt (1% aqueous solution)
20mff saponin (10%
Aqueous solution) 30IIIQ Similarly, the exemplary dye of the present invention (4
), samples containing exemplified dyes (5) and (8) and comparative dyes (A) and (B) used in Example 1 were prepared, and designated as samples 7.8.9 and 1O, respectively. .

Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using a developer and fixer having the following compositions. Development was carried out at 20°C for 1.5 minutes, fixation was carried out at 20°C for 2 minutes, water washing was carried out at 20°C for 5 minutes, and then dried.

(Developer composition) Hydroquinone 159 formaldehyde sodium bisulfite adduct 559 anhydrous sodium sulfite 3g sodium carbonate (-
809 Boric acid 5g Potassium bromide 2.5g Sodium ethylenediaminetetraacetic acid 2g Add water
1.000 heavy a (isolated liquid composition) Sodium thiosulfate 160g Anhydrous sodium sulfite 149 Glacial acetic acid
121112 Borax
129 potash alum
Add 5g water
Ten sheets of each sample subjected to the 1,000+12 development process were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 2 below.

In the sample using the comparative dye, color staining was observed in the sample, but with the dye of the present invention, there was no color stain at all due to excellent run-off and decoloring properties.

Example 3 A silver chlorobromide emulsion containing 70 mol % of silver chloride and 30 mol % of silver bromide and having an average grain size of 0.3 μm was prepared.

After adding 20 mQ of formalin (1% aqueous solution) and 50 mff of saponin (10% aqueous solution) per 1 kg of this emulsion (containing 48 g of silver and 759 g of gelatin), it was coated on a subbed-treated polyethylene terephthalate film support, and then A protective layer having the following composition was coated on this emulsion layer.

(Protective layer composition) Gelatin 409 water

9601Il Formalin (1% aqueous solution) 12IIQ Saponin (10% aqueous solution) 30+I
QNext, on the back side of the support coated with the emulsion layer and protective layer, a gelatin layer containing the dye of the following composition is applied to a dry film thickness of 3 μm.
It was applied so that the thickness was m. (Same as sample 11) (Gelatin layer composition) Gelatin 509 water

835mQ Exemplary dye (12) according to the present invention (2% aqueous solution) 100mQ
Formalin (1% aqueous solution) 15+ff
Saponi 7 (10% aqueous solution) 50+*
Similarly to ff, instead of the exemplary dye (12) of the present invention,
Samples were prepared using the exemplified dye (13) and the following dye (C) and designated as samples 12 and 13.

Comparative dye (C) Developed in the same manner as in Example 2 above, and 10 samples were prepared for each sample.
The sheets were stacked one on top of the other and colored contamination was evaluated. The results obtained are shown in Table 3 below.

Table 3 As shown in the above table, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes of the present invention. Furthermore, it was found that the dye of the present invention can produce a photosensitive material having an excellent antihalation effect without causing any adverse effects such as fogging or desensitization on photographic emulsions.Example 4 Polyethylene Coating A color photographic material was prepared by sequentially depositing the following layers on a paper support -I- from the support side (Sample 14).

1st layer...yellow coupler; α-pivalyl α-(1-
benzyl-2-phenyl-3,5-dioxotriasilidin-4-yl)-27-chloro-57-[γ-(2,
Blue-sensitive silver halide emulsion layer (9) containing 4-di-t-amylphenoxy)butyramide]acetanilide, a hardener (dichlorotriazine) and a surfactant (saponin)
A silver chlorobromide emulsion containing 0 mol% silver bromide, sensitized using a sensitizing dye) was coated with a silver amount of 3,5119/1.
00cm "It was set up so that it would roar.

Second layer: A gelatin layer (intermediate layer) was provided.

Third layer...magenta coupler; i (2,4,6-
+-lichlorophenyl)-3-C3-(2,4-dit
-Amylphenoxyacetamide)benzamide Ku 5
-Pyrazolone, lii! A green-sensitive silver halide emulsion layer (silver chlorobromide emulsion containing 80 mol% silver bromide, containing a film agent (dichlorotriazine) and a surfactant (saponin),
sensitized using a sensitizing dye,) with a coating silver amount of 4,
5m9/], 000cm”.

4th M: A gelatin layer (middle layer) was provided.

No. 5111...Cyan coupler: 2,4-dichloro-
A red-sensitive silver halide emulsion layer containing 3-methyl-6-(2,4-di(-amylphenoxyacetamide)phenol, hardener (dichlorotriazine) and surfactant (saponin) (75 mol% A silver chlorobromide emulsion containing silver oxide, sensitized using a sensitizing dye) was prepared so that the amount of coated silver was 2.0!119/100 cm2.

Sixth layer: A gelatin layer (protective layer) was provided.

Furthermore, a 2% aqueous solution of the exemplary dye (11) of the present invention or the comparative dye (C) was added at a rate of 200 n+d per 1 kg of emulsion.
Sample 15 and Sample 16 were prepared in the same manner as Sample 14, respectively.

These samples 14, 15 and 16 were exposed and then processed according to the processing steps described below.

Processing steps (31'C processing time 1, color development 3 minutes 2 degrees, bleach constant M 1 minute 3, water washing 2 minutes 4, stabilization 1 minute 5, water washing 29) Used in each processing step 1. Processing liquid composition is as follows.

[Color developer composition]

4-Amino-3-methyl-・N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8g Anhydrous sodium sulfite
4.0g Hydroxylamine l/2 sulfate 2.09 Anhydrous potassium carbonate
28.09 Potassium Bromide
1.5g potassium hydroxide 1.
09 Add water to make IQ.

[Bleach-fix solution composition]

Ethylenediaminetetraacetic acid ferric salt 65.09 Ethylenediaminetetraacetic acid disodium salt 3.09 Anhydrous sodium sulfite 9.5. iI Ammonium thiosulfate 77.59 Anhydrous sodium carbonate 4.0g Add water to make 1Q.

[Fixer composition]

Glacial acetic acid 91 Acetic acid
Rium 39 Add water to make IQ.

The density of the unexposed area of each sample after processing is shown in Table 4.Table 4As is clear from Table 4, the samples containing the dye of the present invention have a higher concentration of dye than the samples containing the comparative dye. No color contamination due to residual color was observed. Furthermore, when the sensitivity of each sample was compared, it was found that the dye of the present invention had extremely little adverse effect on the emulsion.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by having a hydrophilic colloid layer containing at least one dye represented by the following general formula [I]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X and Y are respectively a cyano group, a carbamoyl group,
Represents a carboxyl group or a carboxylic acid ester group, R_
1 and R_2 each represent a substitutable group, R_3 and R_4 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R_3 and R_4 may form a ring. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. ]