JPH02259753A - Silver halide photographic sensitive material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to silver halide photographic materials.
9, particularly relates to a silver halide photographic material having a dyed hydrophilic colloid layer.

Conventional technology In silver halide photographic light-sensitive materials, there is a specific
iI$1. Coloring of photographic emulsion layers or other layers is often used to improve color contrast.

When it is necessary to control the original spectral composition incident on the photographic emulsion layer, a flesh-colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion.

This type of coloration is called a filter layer, and when there are a number of photographic emulsion layers, such as in a zero-weight one-color photosensitive material,
A filter layer may be located in between.

Photographic emulsion J - The elements that are scattered after being completely transmitted or transmitted are reflected at the interface between the emulsion and the support, or at the surface of the light-sensitive material opposite to the emulsion, and enter the photographic emulsion layer again. Image blur based on Halley 7
For the purpose of preventing 1 color, a flesh-colored nozzle is provided between the photographic emulsion and the support, or on the opposite side of the support from the photographic emulsion.

Such a coloring layer is called an anti-halley layer. When there are multiple photographic emulsion nos, such as a heavy color-sensitive material, a hareshi prevention no is sometimes placed between those nos. Image sharpness based on original scattering in the photographic emulsion layer. decrease in degree (
In order to prevent this phenomenon (generally called irradiation), photographic emulsions are sometimes washed. These layers to be colored often consist of hydrophilic colloids, and therefore In order to color the layer, a water-based dye is usually included in the layer.This dye must satisfy the following conditions.

(1) It must have an appropriate spectral absorption (1c) depending on the purpose of use (2) It must have a sufficiently low absorbance (3) It must be photochemically inert. In other words, the silver halide emulsion I- (4) (Photographic emulsion) No adverse effect on performance in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog. (Photographic emulsion) When added to a coating solution, it should not cause an increase in viscosity and cause coating failure. (6) In the photographic processing process. , be bleached or dissolved away to leave no harmful coloring on the photographic material after processing.

In order to satisfy these conditions, many dyes that completely absorb visible light or ultraviolet light have been proposed. Especially 70011! In photographic elements sensitized to depths below It, triarylmethane and oxonol-based treatments are widely used for the image improvement purposes described above.

10,000, In recent years, on NFC recording materials sensitized in the infrared region, such as photographic light-sensitive materials used as recording materials that record the entire output of a modern laser, anti-halation and irradiation methods that absorb in the infrared region have been added. There was a demand for the development of a preventive dye.

For example, in one of the four-dimensional methods for producing such photographic materials, an original image is prepared as a set, and a g-element is performed on the halogen-recorded photographic material based on the image, and a negative image or a positive image corresponding to the image of the original image is created. 2. Description of the Related Art A so-called scanner-only image forming method for image preservation is known.

A semiconductor laser is most preferably used as the recording light source for this scanner type.

This semiconductor laser is small, inexpensive, easy to modulate, has a longer lifespan than other K-Ne lasers, argon lasers, etc., and emits light in the infrared region. The advantage of this method is that a bright safelight can be used, making handling easier.

Regarding such dyes for photosensitive materials that are sensitive to the infrared region, please refer to CO Unexamined Patent Publication No. 5O-1 (No. 30116, No. 61-1745).
No. 40, and indoors specified in No. 62-3250 =
IJ dye charge is used as a dye for infrared absorption and (rumor)
2-carbamoyl-1- specified in No. 55-21096 and Research Disclosure No. 22338.
It has been described that infrared dyes can be formed from naphthol couplers and color developing agents in hydrophilic colloids.

However, the above indoaniline dye (a) has poor stability over time, insufficient decolorization during photographic processing, and low absorbance, so it is difficult to develop sufficient effects. They have disadvantages in that they require a fairly large amount of dye and are not photochemically inert, resulting in desensitization or increased fog.

Furthermore, when indoaniline dye is added to the coating solution (photographic emulsion), does it increase the viscosity? As a result, there were many cases of deafness that could not be applied.

In addition, since the infrared dye formed from the 2-carbamoyl-1-su7tol in the upper ml (b) and the color developing agent is water-insoluble, it must be oil bath-compatible when incorporated into the hydrophilic colloid. These colors require the use of solvents, resulting in undesirable phenomena such as an increase in film thickness and a decrease in film strength.Furthermore, these colors However, it has the disadvantage that it is difficult to elute and decolorize.

Therefore, conventional dyes meet the above-mentioned conditions required of them, (
Since there is no dye that can satisfy all of υ~(ψ, there has been a desire for a dye for photographic materials that takes advantage of the characteristics of a semiconductor laser having the excellent performance t- as described above.

(Q) Purpose of the Invention Accordingly, the purpose of the present invention is to provide a photographic light-absorbing water-based indo-aniline system that satisfies the above-mentioned conditions (1) to (Q) and has excellent irradiation and halley scene prevention and filter effects. An object of the present invention is to provide a silver halide photosensitive material having a hydrophilic colloid J- colored with a dye.

0 Structure of the Invention As a result of extensive studies on water-soluble indoaniline dyes, the present inventors determined that the following characteristics are obtained from a hydrophilic colloid containing at least one dye represented by formula (I): This was achieved using silver halide photographic materials.

General formula (I) where R is at least one sulfo! aryl i (e.g. 2-13- or 4-sulfonenyl group, 2.
5-disulfo or 3.5-disulfophenyl group, sulfonaphthyl group, etc.).

J and R may be the same or %, hydrogen atom or substituted or unsubstituted alkyl group (carbonate e
, 1 to 5 lower alkyl groups (e.g., methyl 6, ether group, propyl i, etc.) are preferable, and may have a substituent (e.g., sulfo, carboxyl, water, etc.) %R.

and R1 are both M! Alternatively, an aromatic ring (eg, benzene ring, naphthalene ring, etc.) may be formed.

R1 is a hydrogen atom, an unsubstituted alkyl group (a lower alkyl group having 1 to 5 carbon atoms (e.g., a methyl group,
It preferably represents an ethyl group, a propyl group, etc.) which may have a substituent (for example, a sulfo group, a carboxyl group, a hydroxyl group, etc.), or a halogen atom.

R,, R, may be the same or different, ii
L-substituted or unsubstituted alkyl groups (lower alkyl groups having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.) are preferred, and those having it substituents such as sulfo groups, carboxyl groups, hydroxyl groups, etc.) (may be).

bl is an alkali metal salt such as Na, an ammonium salt, or an organic ammonium salt such as triethylamine, tributylamine, pyridine, and On is 3 or 4.

Although the silver halide X-sensitive material colored with the dye of the present invention represented by the above-mentioned formula (I) has a broad absorption band in the target longitudinal region, other There is almost no unnecessary side absorption in the wavelength region of Excellent prevention of irradiation in the amount used.
Halesin prevention and filter effects can be fully demonstrated.

In addition, after the development process, the dye is completely and quickly decolored and eluted from the photosensitive material, so the finished photographic image contains
In addition to the residual fc dye contained for the above purpose,
Color contamination due to recoloring of decolorizing dyes, and furthermore, re-dying due to the coloring of the developing solution cannot be tolerated.

Furthermore, the dye of the present invention does not undergo changes such as discoloration or fading during the preparation of the dye solution, and is not affected by external conditions such as moist heat during the preparation of the photographic emulsion or during subsequent storage. It has the advantage of being very stable. Furthermore, the indoaniline dye of the present invention is (photographic emulsion) 3I! When the cloth was warmly moistened, no increase in viscosity was observed, and no irregularities were observed.

Next, representative examples of the dyes of the present invention represented by the general formula (!) will be given.

&C2 λ 80 KO, S CC bird) 4 (C salt) a SO, K - The compound represented by the formula (I) is disclosed in JP-A-50-10011
As described in Specification No. 6, Bara, it can be easily synthesized by a method of condensing α-naphthols or salicylic acids, p-phenylenediamines, a t base, and a fertilizing agent. As a more convenient method, it can be easily synthesized using a nitroso compound [-Formula (6)] ・R4 bird - Formula @ / \ 4R1 R, R, #R,, M and n in the reaction warrior is - formula C
In I), examples 1. (
Synthesis of Exemplified Compound 2) [Intermediate (a); Synthesis of N,N-diethyl-3-sulfopropoxyaniline sodium salt] Inpropatool 7
95 powdered soda 12.6#t in 00d
-N after dissolution.

N-diethyl-m-aminophenol 49.6 J'.

36.7 F'i of propane sultone was added and heated under reflux for about 2 hours.

After cooling to room temperature, the precipitated crystals were collected, washed with isoprotetrapanol, and dried to give 78JF of the hygroscopic intermediate (a).
Obtained 〇 [Synthesis of intermediate (E4; N, N-diethyl-4-nitroso-3-sulfopropoxyaniline) Intermediate (a) 78Jlt-130d was dissolved in water and reacted with ice water.
While cooling the ei, add 1271dt of concentrated hydrochloric acid. Keep the internal temperature below t2℃ and add sodium nitrite 1 while stirring.
8.4j was dissolved in 70 dK of water, and a solution was added dropwise little by little.

After stirring at the same temperature for about 2 hours, the precipitated crystal t-F was collected, thoroughly washed with methanol, and dried to produce an intermediate (O yield: 60 J', melting point: 221°C [Example e
Synthesis of Product 2] 2-(4'-sulfophenylcarbamoyl)-1-naphthol triethylamine salt 44.54F.

To the intermediate was added 1 oz of methanol and 1 oz of triethylamine to 31.7 N, and the mixture was heated and refluxed for about 2 hours. After the reaction, 591' of potassium acetate was added to precipitate crystals. 90 Synthesis Example 2 (Synthesis of Exemplary Compound 5) 2-(3'-sulfophenylcarno(moyl)-1-naphthol triethylamine salt) 44.5N.

and an intermediate (synthesized according to the synthesis method → 9N,N-dimethyl-4-nitrone-3-sulfopropoquiquaniline 28.8F to methanol 1) and triethylamine 10
．． After the reaction, 70j”i of potassium acetate and 22 methanol were added to the reaction solution and heated under reflux for about 3 hours.
Add the solution dissolved in 00d, heat it, let it cool, and precipitate crystals. I got an F.

The mixture was thoroughly washed with methanol and dried to obtain the target exemplified compound 15.

In order to add the dye of the present invention represented by formula (1) to the silver halide photographic emulsion or to the Lloyd's solution,
Mizuhiro armpit or methanol, ethanol, cellosolves,
As a solution of glycols, dimethylformamide, dimethyl sulfoxide, pyridine, etc., or as a mixed solution of these organic solvents and water, it can be used in emulsion layers, free coating layers, subbing layers, interlayers, a-retention layers, and ultraviolet absorbing layers. can be added to make it exist.

The amount of these dyes to be used differs depending on the type of photosensitive material to be used, but in general, the area of the photosensitive material is 17F+', 10~
Silver halide photographic emulsions in which the dye of the present invention is used include, for example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver iodobromide. There are emulsions such as silver.

Further, the silver halide photographic emulsion in which the dye of the present invention is used can be spectrally sensitized with commonly used cyanine or merocyanine dyes, etc. Furthermore, it can be sensitized with a polymer rich in amino groups or ammonium groups, a nitrogen-containing emulsion, etc. by a known method. Basic mordants such as polymers containing heterocycles, stabilizers and their precursors,
Additives such as surfactants, hardeners, ultraviolet absorbers, fluorescent brighteners, developing agents and their precursors, etc. can be included.

When silver halide photographic emulsions are used in color photosensitive materials, do they require color couplers or their dispersants? It can also be included.

In addition to gelatin, protective colloids for silver halide emulsions include gelatin derivatives such as heptalated gelatin and malonated gelatin, water-bathable polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and starifying agents for dimensional stability. , latex polymers, etc. can be added to the silver halide photographic emulsion in which the dye of the present invention is used, baryta paper, resin-coated paper, synthetic paper, natural or synthetic polymer films such as cellulose triacetate-based or polyester-based. It can be applied to a support such as.

Next, the present invention will be described in more detail with reference to Examples.

Example 1 1.55 #i of gelatin was added to 15.0 mj of water to swell it, and then heated to 40.0°C to dissolve the gelatin.

To this gelatin bath solution, a hydrolyzed solution of the dye of the present invention and a comparative dye (described later) (2.0 x 10-''4 mol/2.0 Ll of water), a surfactant, and a surfactant were added, and then all of the water was added. Total gold production 4
It was set to 0.0d. Next, this pickled color was coated on a polyester film base that had been undercoated at 7°C at a coating weight of 801/g. The thus obtained Tani sample was heated at 50°C for 1 day.

After each sample was immersed in D-72 developer at 30°C for 5 seconds and 15 seconds, it was washed in running water for 10 seconds, and the layered water droplets were
It was blotted with F paper and dried to obtain a treated sample.

The optical density and density change of the sample and the treated sample at 600 to 900 nm were measured using a dual wavelength/double beam self-recording spectrometer (UV-3000) manufactured by Shimadzu.

The obtained results are shown in I-1.

Comparative dye B Comparative dye D H, C, C, H4S O, K As is clear from Hoechst's N Filter Blue Clean 91, the dye of the present invention has a higher concentration (absorption intensity) of treated iσ and is higher than the comparative dye. It can be seen that the concentration at 780nna is higher than that at 780nna.

Furthermore, it can be seen that the dye of the present invention has excellent decolorization and elution properties from black ink with a low residual color rate.Furthermore, the comparative dye C
The viscosity increases little by little during the preparation of blood eA, and streaks are observed during application.
However, no such phenomenon occurred.

Example 2 1% aqueous solution of dye of the invention 2.3.5.6.9 t10%
In addition to the water-soluble gelatin, add 10% saponin to the gelatin water 1Q15 so that the optical-k at 789nmvc is 1.0 as Sol/Go's mixture.
5d for 0d, 10% formalin gold 1.5d7J11
The same procedure as in Example 1 was carried out using the colored gelatin solution, and a hardened layer with an optical density of 1.0 was obtained.0 This 31! ! A pure silver bromide emulsion was coated on the s layer and developed at 20'C for 90 seconds using developer g having the following composition, followed by fixation, washing with water and drying according to a conventional method.

The chemical resistance of the obtained treated film was determined by the method described in Example 1, and it was found that the dye a3 of the present invention was 5.6.9.
Once after treatment of the sample obtained using K- all 0,0
1 〇 development throat set〉 Metol 3I Sodium sulfite 451 Hyde μ quinone 12j' Sodium charcoal plate (1
water salt) 801 potassium bromide
21 I will raise the sword and make the extra person Gono.

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) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents an aryl group having at least one sulfo group, R_1 and R_2 may be the same or different, and a hydrogen atom, or represents a substituted or unsubstituted alkyl group, and R_1 and R_2 may be bonded to each other to form an aromatic ring. R_3 is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkoxy group or halogen atom. R_4 and R_5 may be the same or different and represent a substituted or unsubstituted alkyl group or a group of nonmetallic atoms necessary for R_4 and R_5 to connect with each other to form a 5- or 6-membered ring. . M represents an organic or inorganic ammonium salt or alkali metal salt, and n represents 3 or 4. )