JPH02251843A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent irradiation and halation and to obtain an excellent filter effect by incorporating hydrophilic layers colored by a specific light absorptive dyestuff into the above photosensitive material. CONSTITUTION:The hydrophilic colloidal layers contg. at least one kind of the dyestuff expressed by formula I are provided on this photosensitive material. In the formula I, R1 to R6 denote an alkyl group; Z1, Z2 denote the nonmetal atom group necessary for forming a benzene condensed ring or naphtho condensed ring; L denotes a substd. or unsubstd. methyne group. While this dyestuff has a high absorption band in a desired wavelength region, the dyestuff has substantially no side absorption in the other wavelength region and does not exert the adverse influence, such as fogging and desensitization, on the photographic characteristics. The excellent prevention of the irradiation and halation and the filter effect are obtd. in this way with the smaller amt. of the dyestuff to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application in the Prison Industry The present invention relates to a silver halide photographic photosensitive material, and more particularly to a silver halide photograph having a dyed hydrophilic colloid layer! & Concerning optical materials.

(8) Prior Art In silver halide photographic materials, the photographic emulsion layer or other JUk layers are colored for the purpose of absorbing the principal in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a color enhancing nozzle is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a color layer is called a filter layer.

When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

When passing through photographic emulsion J- or after being transmitted, the nine elements scattered are reflected at the interface between the emulsion layer and the support, or at the bottom surface of the light-sensitive material opposite to emulsion 1, and then reflected back into the photographic emulsion; In order to prevent blurring of images caused by the incidence of light, that is, haley scenes, a layer is provided between the photographic emulsion layer and the support, or on the side of the support opposite to the photographic emulsion layer. nru.

This kind of coloring-free layer is called a stain prevention layer. When there are a plurality of photographic emulsion nos, such as heavy J-color bad source material, a 7-7W run prevention no may be placed between those nos.

Decreased image sharpness due to light scattering in photographic emulsions (
This desk urine is generally called irradiation)
- To add color to the photographic emulsion layer, the color of the photographic emulsion layer is increased. Usually, a water-bathing group is included in the layer.

This dye needs to satisfy the following conditions.

(1) Must have appropriate spectral absorption for the purpose of convenience.

■a The luminous intensity is sufficient.

In other words, silver photographic emulsions J- containing halogens have an adverse effect in a chemical sense, such as a decrease in sensitivity, regression, or fog. There isn't.

(4) (Photographic emulsion) Blood grade: No change in color over time such as fading during manufacturing or emulsion manufacturing or storage. Do not cause a route failure condition by ascending the road.

(6) In the photographic processing process, there should be no residual color increase on the photographic A photosensitive material after decolorization (n1) (7) The color must not be increased using the photographic processing liquid KR4 dye.

Conditions like this? To meet this requirement, many dyes that absorb visible or ultraviolet light have been proposed.

In particular, in recent years, the development of anti-halation and anti-irradiation dyes that absorb in the visible region for use in photographic light-sensitive materials as recording materials for recording laser output has become cheaper.

For example, one of the methods for repairing such photographic light-sensitive materials is to completely run the original image, and then, based on the image shown in step 7, perform a slanting operation on the silver halide X-sensitive material to form the entire image of the original image. A so-called scanner-only image forming method is known.

A light emitting diode, a Kie-Ne laser, or an argon laser is often used as a light source for this scanner-only hC recording.

Regarding dyes for photographic light-sensitive materials having high photosensitivity in the visible region, for example, JP-A-6O-218b 41, 1
0” Showa 6 0. - 1 3 5 9 3 7, 10
J62-185755, Sho 62-273527, Sho 63-139949, etc., but these known dyes are long enough to absorb light of 633 nm and 670 nm, and are stable over time. 7 tons, insufficient bleaching during the photographic processing process, and even with bleaching, the treated area is colored, and the absorption capacity is low, so a fairly large amount of dye is required to achieve a sufficient effect. Or, because it is not photochemically inert, it may cause an increase in texture or fog, and it may increase the viscosity of the coating solution, making it impossible to coat. There is no material that satisfies all of the conditions (1) to (7) above, and for this reason, a dye for the above-mentioned laser-fixed photographic material has been desired.

(C)@Ming's purpose Therefore, the purpose of the present invention is the above-mentioned Zhuhan a] ~ (7)
(- Adding immediately r'L7'ic radiation and anti-halation and filter effect seven M water-bathable photographic absorption 0 0 Structure of the Invention Necessary by Providing Original Materials The present inventors have conducted extensive studies on water-soluble dyes, and the purpose of the present invention is to obtain at least one of the dyes represented by the following general formula (1). Must have a hydrophilic colloid containing M.
- found to be achieved by a silver halide photographic light-sensitive material having the following characteristics: R2,'m, ,
R1s a, may be 1 kJ- or the same alkyl it-, 't'fc%R! RbiR1
, or with the carbon atoms to which they are bonded to Rs & R6! I! You may also indicate i,
2, and 2. ; f: 2″L-e!L indicates the non-metallic atom essential for forming a naphtho-fused ring in the unsubstituted benzo-fused ring. However, R1, R, . Zl,
Among these, the group represented by Zl preferably has at least 4 to 6 flR substituents (for example, a sulfonic acid group, a carboxylic acid group, or a phosphoric acid group), and particularly preferably has 4 to 6 dye molecules. sulfonic acid group 'k”ff
represents a group 2 that allows

In the present invention, a sulfonic acid group means a sulfo group or a salt thereof, and a carboxylic acid group means a carboxyl group or a salt thereof. Examples of salts include alkali metals such as Na, diammonium salts, triethylamine, tributylamine, pyridine, etc.
can be mentioned.

L represents a substituted or unsubstituted methine group.

R1 and R1 preferably represent a carbon atom having 7 sulfonic acid groups.
Lower alkyl i of numbers 1 to 5 (e.g. 2-sulfoethyl M
, 3-sulfopropyl group, 4-sulfobutyl group, etc.).

The alkyl group represented by R*, a, , R@, R@ is preferably a lower alkyl group of μ-order formulas 1 to 5 (e.g., methyl group, ethyl group, n-propyl M, n-butyl group, ingropyl group) As n-pentyl group, etc.), R, and R8 or R.

and R6 may form 7-chloroalkyl i (eg, cyclopentyl group, cyclohexyl group, cyclohegetyl group, etc.) together with the carbon atom to which they are bonded.

The substituents of the benzo-fused ring formed by 4 non-gold lI atoms represented by zs, Zz, and 9 μ naphtho-fused ring include one sulfonic acid group, a carboxylic acid group, a hydroxyl group, a halogen atom (e.g. F, CJ, Br, etc.) cyano group, substituted amino group (e.g. dimethylamino group, diethylamino group, ethyl-4-sulfobutylamino group, di(3-sulfopropyl)amino group, etc.), or directly or Consolidation of values 2! i! Carbon ridges 1 to 5 alkyl groups bonded to the ring via i and substituted with 7ctit or directly substituted with S [e.g., methyl group, ethyl group, propyl group, butyl group, etc. (substituents include sulfone, carboxylic acid group, hydroxyl group, etc.) The linking group of 211iu is, for example, -〇--NHCO--NH8Ot--N)iCL)0--
NRCONI-1--COO--CO--80, -1, etc. are preferred.

As the base group of the methine group represented by L, carbon ridge 1 to
Substitution of 5 or no t! lower alkyl group (e.g. methyl group, ether group, 3-hydroxy7'ak:J
, /<ndyl group, 2-sulfoethyl group), halogen atom (e.g. F, C), Br, etc.) An alkoxy group (Nj is a methoxy group, an ethoxy group, etc.) is preferred. Also, it does not matter if the substituents of the methine group represented by L are combined to form a 6-membered chain (for example, a 4,4-dimethylcyclohexene ring) rich in three methine groups.

Although the color-enriched halogenated catfish photographic material of the present invention represented by the above general formula (1) has a molecular extinction coefficient of gold in the target reformation region, , other wavelength regions have almost no unnecessary sub-absorption, and historically,
To fully demonstrate the effect of preventing fuzzy layering, swelling, and swelling while minimizing the risk of fogging, g-sensation, and other custom-made photographs. I can do it.

In addition, after the development process, the dye is completely and quickly decolorized from the photosensitive material, so that in the finished photographic image, not only the residual dye contained for the above purpose but also the color due to the recoloration of the decolorized dye are retained. Further, the dyes of the present invention do not cause any changes such as discoloration or fading during the preparation of the dye bath, and are not found in photographic emulsion 1iI4. It has the advantage that it can be maintained without being affected by external conditions such as heat and humidity during storage and subsequent storage.

Furthermore, the dye of the present invention can be used in (photographic emulsion) V? −
= At 9 o'clock, no increase in viscosity was observed and no blood 4A symptoms were observed. The scope of the invention is not limited to these.

(I-1) (I-4) (I-5) (I-9) (I-6) (I-10) (I-11) (I-16) (I-18) CI-14) Next Eight specific synthetic examples of dyes represented by formula (I) will now be described.

Synthesis Example 1 (Synthesis of dye!-2) 1'-(3-sulfopropyl)-2'-methyl-5! −
Sulfospiro [cyclohexane-1,3'-(3'H)
- Indolecotriethylammonium 5.03N methanol 60d methanol, triethylamine 2.80m and malondialdehyde cyanyl hydrochloric acid *1. aoy, and added dropwise 1.0 d'i of acetic anhydride. Stirred at 90' iIi temperature for 3 hours and 4 hours. The formed precipitate was taken and re-crystallized with aqueous ethanol to give 2.2!it-dark blue crystals of dye I-2.Melting point: 300°C or higher λrn*x 660mm (g=17.3X10
) Synthesis Example 2 (Synthesis of Dye 1-8) 1-(3-sulfopropyl)-2,3,3-trimethyl-5-sulfindolenine triethylammonium 4.
63N methanol 70ILIIIQ bath with triethylamine 2.79JIJ and malondialdehyde cyanyl salt &1! ! Add 1.30j' of 2-salt and dropwise add 1.0- of acetic anhydride. After stirring at room temperature for 2 hours, 4.9 I of potassium acetate was added to 60 dfiii of ethanol, heated and refluxed for 10 minutes. Returned to room temperature for 90 minutes. The resulting precipitate was collected, washed with ethanol, and recrystallized with Amagi ethanol to obtain the dye. Dark blue crystals of I-8 2.0g'ii-obtained 90 Melting point 290°C (decomposition)
λmax 648 nm (8:16.l
As a bath liquid of t4g of water, or methanol, ethanol, -kosolfs, glycols, dimethylformamide, etc., or as a knitting bath liquid of these Km's and water, emulsion no, back layer, bottom. It is possible to make 4 types by adding air to the ultraviolet absorbing layer.

The number of violets used for these dyes varies depending on the commonly used photographic layer, but generally 1 to 1. υ0υ
The blood is pumped so that it becomes hard.

Examples of silver halide photographic emulsions in which the dyes of the present invention can be used include emulsions of silver chloride, silver bromide, silver halide, silver iodobromide, and the like.

Further, silver halide photographic emulsions in which the dye of the present invention is used are disclosed in JP-A-59-191032 and JP-A-59-192242.
, 1982-108241, etc., which are commonly used cyanine and merocyanine dyes. Further, by a known method, a basic mordant such as a polymer containing a polytwo-containing violet heterocycle containing an amine jIj or anthtnium group, a stabilizer and its precursor, a surfactant, a hardening agent, and an ultraviolet absorber. , a fluorescent brightener, a developing drug and its precursors, and the like.

When a silver halide photographic emulsion is used in a color light-sensitive material, a color coupler or a dispersion array thereof can also be used.

In addition to gelatin, protective colloids for silver halide emulsions include gelatin fermentation conductors such as heptalated gelatin and malonated gelatin, water-bathable polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizers for dimensional stability. agents, latex polymers, etc.

Further, the silver halide photographic emulsion in which the dye of the present invention is used can be applied to a support such as baryta paper, resin-coated paper, synthetic paper, natural or synthetic polymeric film such as cellulose triacetate-based lubricant or polyester thread. 0 Next, the present invention will be described in more detail with reference to Examples.O ■ Lol Examples Example 1 Gelatin 1.5! Mi water15. After swelling with Om, gelatin was heated to 40.0°C and dissolved in f#.To this gelatin solution, the dye of the present invention and a comparative dye to be described later were mixed with water i.
11'gli (1,Ox 10-'%7I/water 2.0
d), a hardening agent, and a surfactant, add water to make the total t 40, Od 90. Next, add this colored mat-,
After applying a subbing layer 'a', it was coated on a polyester film base so that the coated layer was 801/g.

The Kutani sample thus obtained was heated at 50°C for 1 day.

Each sample was immersed in D-72 working solution at 30°C for 5 seconds and 15 seconds, then washed under running water for 10 seconds, the attached water droplets were sucked up with a door paper, and the treated samples were dried. And so.

λmm at 600-900 nm for samples and processed samples
The optical density and density change in x were measured using a Shimadzu dual wavelength/double beam self-recording spectrophotometer (UV-3000).

The obtained request is shown in 2-1.

Comparative dye A Comparative dye B Comparative dye C From Table 1, dyes (1) and (5) of the present invention are superior to comparative dyes A-D in optical density before treatment and residual color rate after treatment. You can see that

Example 2 A silver iodobromide emulsion was prepared using rhodium salt in a high contrast amount,
After chemical ripening, near-infrared sensitizing dye, stabilizer, hardener,
Make-up was done by adding a surfactant. Safe! -2 on polyethylene laminate paper with gelatin coating solution of iJ-.
A blank sample was prepared by applying the dye used in Example 1 to the emulsion layer at 1rr? Ah next ji 0.0
Six types of samples were prepared in the same manner as the blank sample, except that they were healed to a concentration of 2 mmol.

Each sample thus obtained was exposed to a LE of 670 nm.
Exposure was performed using a D light source, development was performed at 30°C for 25 seconds using a regular PQ developer, and the process of cleaning, washing, and drying was performed using an automatic gold developing machine.

Tomo evaluates image quality on a five-point scale from 1 (very poor image quality with lots of fringes) to 5 (extremely sharp image with no fringes). The residual color was evaluated on a five-point scale from 1 (very much residual color) to 5 (no residual color at all).

The result is shown as t-thorn-2.

Table 2 From the results in Table 2, it can be seen that Samples 1 and 2 of the present invention have good image quality, no residual color, and little adverse photographic effect.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material characterized by having a hydrophilic colloid layer containing at least one dye represented by the following general formula. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_4 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and R_
2, R_3, R_5 and R_6 may be the same or different from each other and represent an alkyl group, and R_2 and R_
3 or R_5 and R_6 may form a cycloalkyl group together with the carbon atom to which they are bonded, and Z
_1 and Z_2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring. However, R_1R_4, Z_1, and Z_2 represent groups that allow the dye molecule to have at least three acid groups. L represents a substituted or unsubstituted methine chain. )