JPS58143342A - Silver halide photosensitive material containing dye - Google Patents

Abstract

PURPOSE:To obtain an entitled material superior in spectral absorption characteristics and decoloring elution tendency in photographic development, and very small in staining after the development, by adding a specified oxonol dye. CONSTITUTION:A silver halide photosensitive material of this invention is formed by adding 1-800mg/m<2> oxonol dye having formulaI(R1 is an aryl group having at least one sulfonate group; R2 is H, lower alkyl, or aryl; and n is 1 or 2), such as formula II, to a hydrophilic colloidal layer, developing its color, and using its layer as a constituent layer of the silver halide photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a dye, and particularly to a silver halide photographic light-sensitive material containing a hydrophilic colloid layer colored with an oxonol dye useful as a light-absorbing dye. 1- It is related to this.

Silver halide photographic material (hereinafter referred to as photographic material)
[k] It is well known that dyes are included in photographic materials for the purpose of absorbing light of a specific wavelength. It is common practice to color the sex colloid layer. For example, a filter layer is usually located in the L layer of the photosensitive emulsion layer or between the emulsion layers, and serves to convert the incident light reaching the emulsion/g into light having a preferable spectral composition. In addition, for the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back surface of the support, so that the interface between the emulsion layer and the support, Absorb harmful reflected light on the back of the support, etc.
Prevent halation.

Furthermore, it is common practice to color the emulsion layer to absorb harmful reflected light and scattered light from silver halide grains, etc., to prevent irradiation.

The dyes used for such purposes must have good absorption spectral characteristics depending on the purpose of use, and must be completely decolorized or easily eluted from the photographic material during photographic processing. In addition, the dye should not cause any residual color staining after development, it should not have any negative effects on the photographic emulsion such as fogging or desensitization, and it should not diffuse from the colored layer to the transparent layer. It must also satisfy conditions such as excellent stability over time in photographic materials and no discoloration or fading.

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 and Japanese Patent Publication No. 39-2206
No. 9 isobarically described oxonol dye, US patent It
Examples include styryl dyes as typified by US Pat. No. 1,845,404, merocyanine dyes as typified by US Pat. No. 2,493,747, and cyanine dyes as typified by US Pat. No. 2,843,486. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in photographic materials.

Among the oxonol dyes known to date are the dyes described in German Patent No. 2,117,346 VC. This Ogisonol dye R is a dye having a carbamoyl group at the 3-position of the 5-pyrazolone ring, but does not contain a sulfo group in its molecular structure and is hardly soluble in water. Photographic processing is usually carried out under low alkaline conditions for a short period of time, and it is difficult for this dye to be completely eluted from the photographic material during processing. Further, the residual dye that has been once decolored may restore its color over time. Therefore, especially when dyes are used in photographic materials coated in multiple layers, a water-soluble group such as a sulfo group is introduced into the dyes to make them water-soluble, and they are easily eluted during the development process to form photographic materials. It is desirable to use dyes that do not remain in the dye. Furthermore, when incorporating dyes into photographic materials, water-soluble dyes can be easily dissolved in water to form an aqueous solution, but poorly water-soluble dyes require the use of organic solvents, etc. , which is also undesirable in terms of toxicity.

An object of the present invention is to provide a photographic material containing a water-soluble dye that has good spectral absorption characteristics, is easily decolorized and eluted during photographic processing, and causes very little staining after processing.

These objects of the present invention have been achieved by an oxonol dye represented by the following formula.

General formula % Formula % In the formula, R1 represents an aryl group having at least one sulfo group, R1 represents a hydrogen atom, a lower alkyl group, or an aryl group, and n is 0. Represents an integer of l or 2.

Specific examples of each group in the general formula 1 above are shown below.

Examples of the aryl group represented by Ro include 4-sulfophenyl group, 3-sulfophenyl group, 2-methyl-
4-sulfophenyl group, 2-chloro-4-sulfophenyl group, 4-chloro-3-sulfophenyl group, 2-chloro-5-sulfophenyl group, 2-methoxy-5-sulfophenyl group, 2-hydroxy- 4-sulfophenyl group, 2
．． 5-dichloro-4-sulfophenyl fi, 2.6-sulfophenyl group, 2.5-disulfophenyl group, 3.5-disulfophenyl group, 4-phenoxy-3-sulfophenyl group , 2-chloro-6-methyl-4
-Sulfophenyl M, 3-carboxy-2-hydroxy-5-sulfophenyl group, 3.6-1 sulfo-α-naphthyl group, 8-hydroxy-3,6-disulfo-α-naphthyl group, 5-hydroxy- 7-sulfo-β-naphthyl f
i, 6,8-disulfo-β-naphthyl group, and the like.

The lower alkyl group represented by R1 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tertiary-butyl group, etc. furthermore, a hydroxy group, a cyano group, a halogen atom (e.g.
Fluorine atoms, chlorine atoms, bromine atoms, etc.), alkoxy atoms (
For example, methoxy group, ethkyne group, etc.), aryloxy group (e.g., phenoxy group, etc.), aryl group (e.g., phenyl group), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), aryl It may be substituted with an oxycarbonyl group (for example, a phenoxycarbonyl group), or the like.

Further, examples of the Ryl group represented by R2 include phenyl group, naphthyl group, etc., and these 7 IJ-
The ru group further includes a hydroxy group, a cyano group, a nitro group, and a halogen atom (for example, a fluorine atom, a fluorine atom, a bromine atom, etc.)
, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, etc.), an alkoxy group (e.g., methoxy group,
ethoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), or aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.).

Typical examples of the oxonol dyes represented by the above general formula include the following, but the present invention is not limited thereto (10 dye 70 0 dye 80 0 -11- 113-12-14- Dye SaeNext, a typical method for synthesizing the oxonol dye according to the present invention will be described.

Synthesis Example 1 (Synthesis of dye 8) 3-carbamoyl-1,-(p-sulfophenyl)-5
-pyrazolone 5,7y and 3-piperidino-2-propenanyl 2. Og in methanol I00++tJ, and triethylamine 5.1. p was added thereto, and the mixture was reacted for 1 hour under heating and reflux. Next, 20ml of methanol
Add 2.9g of potassium acetate dissolved in K, and then add K 1
Stirred for 0 minutes. After cooling, the precipitated crystals were collected by filtration, washed with methanol, and dried to obtain 4.7 g of the desired dye.

The λmix of the aqueous solution of this dye was 544 nm.

Synthesis Example 2 (Synthesis of Dye 17) 3-carbamoyl-t-(p-sulfophenyl)-5-
5.7 g of pyrazolone and 2.39 g of 5-piperidino-2,4-pentadienyl were placed in 100 d of methanol, and 5.19 g of triethylamine was added thereto, stirred at room temperature for 5 hours, and further heated to reflux. The reaction was continued for 15 minutes. Next, potassium acetate dissolved in 20 ml of methanol 2.
9 g was added and further stirred for 5 minutes at Vc. After cooling, the precipitated crystals were collected by filtration, washed with methanol, and dried.4.
6 g of the desired dye was obtained.

The dyeing aqueous solution Cλmax was 635 nm.

In the photographic material of the present invention, the oxonol dye represented by the above general formula can be incorporated into a silver halide photographic emulsion and used as an irradiation-preventing dye, or can be used as an anti-irradiation dye in a non-photosensitive hydrophilic colloid layer. It can also 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 according to the present invention into a halogenated photographic 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 of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution is added to a coating solution and coated by a known method to contain the dye in the photographic material. It's hard to let it happen. The content of the dye in the cornea varies depending on the purpose of use, but in general, it should be applied in an amount of 1 to 800 dyes per liter of area on the photosensitive material.

Supports in the photographic material of the present invention include cellulose acetate, cellulose nitrate, e.g. polyethylene terephthalate) [1'] polyester film, e.g. polyolefin film such as polyethylene, polystyrene film, polyamide film, polycarbonate film, Examples include baryta paper, polyolefin-coated paper, polypropylene synthetic paper, glass plate, metal, and the like, and these supports are appropriately selected depending on the intended use of the photographic material.

Examples of hydrophilic colloids in the photographic material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alkinoic acid, and tate such as polyvinyl alcohol and polyvinylpyrrolidone. Examples include cellulose derivatives such as starch fat and carboxymethyl cellulose, and these can be used alone or in combination.

18- As the silver halide emulsion in the photographic material of the present invention,
Any of those commonly used in silver halide photographic emulsions, such as silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver iodobromide, are included.

The silver halide emulsion used in the photographic material of the present invention can be prepared by various manufacturing methods, including the usual manufacturing method.
No. 6-7'172, or as described in U.S. Pat. No. 2,592,250, i.e., at least a portion of the A method for producing a so-called convergence emulsion in which an emulsion of silver salt grains consisting of a silver salt is formed, and then at least a part of the grain force is converted into silver bromide salt or silver iodobromide, or can be created. This silver halide emulsion contains chemical sensitizers such as thiosulfate, thiolyl chloride, thiourea, allyl isothiocyanate,
Sulfur sensitizers such as cystine, active or inactive selenium sensitizers, gold compounds such as potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiol methyl chloride, ammonium palladium compounds such as chlorobaratate, sodium chloropalatite, etc., platinum compounds such as potassium chloroaurate, noble metal sensitizers such as ruthenium compounds, rhodium compounds, iridium compounds, etc.; This emulsion can be sensitized using a combination of sensitizers.
In addition to chemical sensitization, radical sensitization can be performed using reducing agents, and stabilization can be performed using triazoles, imidazoles, azaindenes, pendzyl zolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. In addition, a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound can be contained.

The photographic emulsion used in the photographic material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary.

Sensitizing dyes include cygammane dye, merocyanine dye,
Complex cyanine dye, oxonol color light, hemioxonol dye, styryl dye, merostyryl dye,
Various sensitizing dyes such as streptocyanin can be used, and one or a combination of two sensitizing dyes can be used.

In the photographic material of the present invention, in the photographic emulsion layer and other hydrophilic colloid layers, glycerin, a dihydroxyalkane such as 1°5-bentanediol, an ester of ethylene bisglycolic acid, and suethoxydiethylene glycol succinate are added by emulsion polymerization. The obtained water-dispersible fine particulate polymer compound can contain wetting agents, plasticizers, film property improvers, etc., and can also contain N- Methylol compounds, mucohalogen acids, divinyl sulfones, 2.4-
Active halogen compounds, dioxane derivatives, divinyl ketones, isocyanates, carbodiimides and other hardening agents, saponins, polyalkylene glycols, polyalkylene glycol ethers, γ Surfactants such as alkyl sulfonate, alkylbenzene sulfonate, and γ-rukylnaphthalene sulfonate, as well as photographic additives such as fluorescent brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers. can be contained.

In the photographic material of the present invention, a color coupler may be contained in the photographic emulsion layer, and the coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for masking or a coupler that releases a color inhibitor. It may be. Yellow-forming couplers include open-chain ketomethylene compounds such as acylacetamide, magenta-forming couplers include pyrazolone compounds, and cyan-forming couplers include phenolic or naphthol compounds.
Usually used to advantage.

Next, the present invention will be illustrated by Examples, but the present invention is not limited thereto.

Example [35 rnl distilled water 3.5 l K gelatin is added and dissolved, to which dyes (L), (8) and (17) according to the invention are added and dissolved.
) for each 2. 5rrLl containing 10”-’mol OX
of water, and then add 1.25 mA of 10% saponin aqueous solution.
and 0.75 ml of 1% formalin solution were added, and water was added to bring the total volume to 50 d. This dye solution was applied to an acetate cellulose support and dried (sample (I), (
11) and (III).

In addition, instead of the dye according to the present invention, the following known dye A,
A comparative sample (
IV), (V), (VI), (Vlr) and (vIff) were created. t, c, comparison sample (■)
Since the known dye is insoluble in water, it was dissolved in methanol triethylamine vinegar solution Vc and added to the coating solution.

Known dyes A, B, and C Known dyes Known dye E Each of these samples was developed with the following composition m K 30°C
After soaking in water for 1 minute, washing with water for a second, and drying.

The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the optical density at the maximum absorption wavelength. The result and the maximum absorption wavelength in gelatin
Shown in the table.

1 (DI is the concentration before immersion in the developer, and D is the concentration after immersion.) Developing solution power composition Metol 3. OI sulfite) lium (anhydrous) 45.0 g Hydroquinone t2. og sodium carbonate (■water salt) 80.0,! i+potassium bromide Add 2.0g water to make 1e.

As is clear from Table 1, the dye according to the present invention has a preferable spectral absorption maximum and exhibits superior decolorizing properties compared to known dyes. Ta. In addition, known dyes (A, B,
In the samples containing C and E), the dye eluted and colored the processing solution, but with the dye according to the present invention, such coloring contamination was not observed. It is not a color dye and has poor decolorizing properties, so it is not suitable for use in the photographic material of the present invention.

Furthermore, known dyes A, B, and C are not preferable because each of them has a short absorption maximum wavelength in gelatin.

Example 2 On a support made of polyethylene-coated paper, the following layers were sequentially formed from the support side to prepare a color photographic material (Sample ■).

1st layer...Yellow coupler; α-Pino (IJ/
α-([-benzyl-2-phenyl-35-dioxotriasilidin-4-yl)-2'-chloro-5'-[γ(2-4-diylphenoxy)].

Tyramide] Acetanilide hardener (-)chlortriazine) and surfactant Blue sensitivity containing sexual agent (saponin) Halogenated emulsion layer (90 malt odor) Sensitized color with silver chlorobromide emulsion containing silver oxide Silver coated with (C sensitized) The amount is 3. sq/too dl.

2nd rWj... Gelatin layer (middle + ikl)
・Established.

3rd layer...Magenta coupler; 1-(2,4,
6-trichlorophenyl)-3-43-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone green-sensitive halogen containing hardener (dichlorotriesterine) and surfactant (saponin) Kasen emulsion 1! (A ground silver bromide emulsion containing 80 mol of silver bromide, sensitized using a sensitizing dye) was pressed so that the coated silver amount was 4.5 7100 d.

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

5th layer... (Cyan coupler; 2,4-dichloro-3-methyl-6-(2,4-di-t-amylphenoxyacetamide) Phenol hardener (dichlortriester) and surfactant A red-sensitive silver halide emulsion layer containing (saponin) (a silver chlorobromide emulsion containing 75 mol of silver bromide, sensitized using a sensitizing dye) was coated with a coating silver amount of 2.0 ■ /100 crl.

6th layer...gelatin layer (protective layer)? Established.

Furthermore, 2% of the dye (8) according to the present invention or the known dye F
A green-sensitive emulsion (third layer coating solution) was prepared by adding 200 mJ of aqueous solution per 1 kg of emulsion, and a sample ISI (X) and a sample (X[) were prepared in the same manner as the above sample (■).

Known Dye F These samples (IX), (X) and (Xl) were exposed and then processed according to the following processing steps.

29- [Processing process (31℃)] Processing time 1, color development 3 minutes 2, bleach-fixing 1 minute 3, water washing 2 minutes 4, stabilization 1 minute 5, water washing 2 minutes Processing solution used in each processing step The composition is as follows.

[Composition of color developing solution]

4-amino-3-methyl-N-4,8g
β-Hydroxyethyl)-aniline sulfate anhydrous sodium sulfite 4.0g hydroxylamine % sulfur i! iR salt2. Oji Anhydrous Potassium Carbonate 28.0.9 Potassium Bromide
1.5g potassium hydroxide
Add 1.09 water to tg.

Hereinafter, Kinpakuno,・1No M--' [Composition of bleach-fix solution] Ethylene diamine triacetate iron jJ 65.0.9
Ethylenediamine triacetic acid-2 sodium salt 3.0. p Anhydrous sodium sulfite 9.51 Ammonium thiosulfate 77.5g Anhydrous sodium carbonate 4.0. ! i! Add water to make up to 1 liter.

[Composition of stabilizer]

Glacial acetic acid 9d Sodium acetate 3I Add water to make 11.

Table 2 shows the density of the unexposed area of each sample after treatment.

Table 2 As is clear from Table 2, in the samples containing the dye according to the present invention, color staining due to residual color of the dye was not observed, as was the case with samples containing known dyes. Furthermore, when the sensitivity of each sample was compared, it was found that the dye according to the present invention had extremely little adverse effect on the emulsion.

Example 3 80 ml of a 1% aqueous solution of the dye (9) according to the invention; 350% gelatin, 10 ml of a 1% formalin solution and 12.5 ml of a 10% aqueous saponin solution
J, add water and bring the total amount to 5QOmI! I made a gelatin solution of binding dye. The above dye coating solution was coated on the back side of a cellulose acetate film support coated with an orthomatically sensitized silver chlorobromide emulsion layer (including silver bromide intermolch) layer and a protective gelatin layer, and the sample (X[ )It was created.

Samples (xr) and (xlV) were prepared in the same manner using the dye (14) of the invention and the known dye F in place of the dye (9) VC of the invention.

After exposing each of these samples (■), (■) and (XIV) to light, they were developed at 27''C for 2 minutes using a developer having the following composition. Thereafter, fixing, washing with water, and drying were carried out using conventional methods.

Composition of developer 33- After processing, the sample (XIV) containing the known dye exhibited a pale pink color and residual color staining was observed due to the dye, but samples 1 and 2 using the dye according to the present invention (■ ) and (XIH)
No dye contamination was observed in the photographic emulsion.The photographic material had no adverse effects such as capri, desensitization, etc. and had an excellent antihalation effect.

Agent Yoshi Kuwahara Beautiful procedural amendment 1981 111129B l Neutral 1st grade 11th grade 5th grade 1st cow 1st grade 263
s 2 'j2 Name of the invention Silver halide photographic material containing dye; 3 Supplement 11
Relationship with Nagisa 11 case 17f lt'l-Applicant I, I
Place Higashihara Toriki 11 C1 Nishi-Shinjuku 1-26-2 Name (+27) Konishi Rokuka'sada+=Gyo Co., Ltd.? 1 Representative Director Nobuhiko Moto 4 Agent Address: 191 1i'i Tokyo H! l1fil+Sakuracho 1
Address 5 Item of supplementary order A.1 Voluntary 6. Column 7 of "Detailed description of the invention" of the specification to be amended. Contents of the amendment The detailed description of the invention is amended as follows.

2- Procedural amendment ゛Mr. Kazuo Wakasugi, Commissioner of Patent J1] Neutral indication Patent application No. 26382 of 1982 Li2 Name of the invention Silver halide photographic light-sensitive material containing dye: (Supplement 11-
Relationship with the case of a person who does Place: Tokyo, Japan! IIf, Nakasakura-cho 1, Konishi Roku, Photography Co., Ltd., 5 Date of supplementary order: 1 Voluntary action 6: Column 7 of Detailed Description of the Invention - 1 of the specification to be amended, Amendment Contents (1) The detailed description of the invention is amended as follows.

After page 15 of the specification, “Dye 6 0 111 H, N-C-C-C=CH-CH=CH-C-C-C-
NH2It l l II 2- 253-

Claims (1)

[Scope of Claims] A silver halide photographic material containing an oxonol dye represented by the following general formula. [General formula] 1R1, (wherein R1 represents an aryl group having at least one sulfo group, the island represents a hydrogen atom, a lower alkyl group, or an aryl group, and n is an integer of 0.L or 2) )