JPH05216155A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic material which is wetted well with a developer without causing contamination with the developer during developing and which does not cause unevenness of coloring density which may be generated in the perforated portion of a 35-mm roll film nor cause fine unevenness of image density due to unevenness of water droplets during washing and drying after the developing. CONSTITUTION:In a photographic material having at least one photosensitive silver halide emulsion layer on a support, poly (N-acylethylene imine)-graft polysiloxane is contained in the silver halide emulsion layer or at least one of the other photograph forming layers.

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 containing a novel surfactant in a hydrophilic organic colloid coating layer, more specifically, a silver halide having improved developability. It relates to a photographic light-sensitive material.

[0002]

2. Description of the Related Art For example, the following frequently occur as a serious problem when developing a photographic film. (1) .Dry unevenness, film stains, uneven density due to adhesion of water-insoluble matter on the transport roller due to processing solution contamination during the development process, (2) .Coloring at the perforation part of the 35mm roll film Density unevenness, and
(3). The occurrence of fine image density unevenness, which is considered to be caused by water drop unevenness during washing and drying after development processing, especially after high-temperature rapid processing, can be mentioned. The background behind each of these issues is described below.

In recent years, a method for reducing the amount of rinsing water at the time of treatment from the viewpoint of environmental protection, water resources, cost, and simplification of treatment equipment, and a method for reducing the amount of replenishing treatment liquid from the viewpoint of cost, and further Attempts have been made to thicken the treatment liquid in order to shorten the treatment time, but with the development of such treatment methods, the above-mentioned treatability has become an important issue. The problem of the processing solution contamination of (1) has been often generated in the conventional photosensitive material having a high silver salt concentration such as X-ray, and the cause thereof is due to the property of the surfactant contained in the photographic photosensitive material. However, there were many. Applications of surfactants used in photographic light-sensitive materials include, for example, coating aids, antistatic agents, emulsifying dispersants, etc., but even if they give good results as their intended functions, they cause processing solution contamination. It was often difficult to apply it to photographic light-sensitive materials.

The problem of (2) uneven color density which occurs in the perforation part of the 35 mm roll film is 35 mm when the photographic film is individually fixed in the vertical direction and sequentially developed (hereinafter referred to as "suspended development"). Color density unevenness may occur around the perforations of the roll film. This is unevenness in color density due to unevenness in drying caused by the liquid remaining in the perforation which has not been dried yet flowing out after the periphery of the perforation of the film is dried during the drying process.

This phenomenon is unlikely to occur when an alkylbenzene sulfonic acid type surfactant is used, and tends to occur when an alkylnaphthalene sulfonic acid type surfactant is used.

On the other hand, when an alkylbenzene sulfonic acid type surfactant is used, there is a problem that the correction liquid is repelled when the image of the film after processing is retouched, or the liquid is easily repelled at the time of immersion printing. A method for solving both of these problems at the same time. Was desired.

The above-mentioned color density unevenness is less likely to occur in the cine-current method processing (development carried out by joining films in a roll shape), and this method is often used in the color negative, but it is a problem in the hanging development method. However, in the case of color reversal films that are often subjected to sensitization processing, the hanging development method is still the mainstream, and it has the above problem.

The problem of (3) generation of water droplet unevenness at the time of washing and drying after high-temperature rapid processing is, for example, in the case of microfilm and comb film, in order to speed up the required development processing speed, coated silver is used. The amount is kept to a minimum. To further increase the drying speed after washing with water for development processing,
A hydrophilic binder or the like (for example, gelatin) coated on the support is also kept in a necessary minimum amount. Moreover,
These photosensitive materials are subjected to high-temperature development processing and then rapidly dried at higher temperatures.
e Roller) squeezing condition or draining plate (Squeeze Bl
If minute water droplet unevenness remains on the surface of the light-sensitive material due to the clearing condition of ade), uneven drying occurs due to rapid drying thereafter, and as a result, minute uneven image density is likely to occur after drying.

Some of the image density unevenness can be observed with the naked eye, but this is out of the question, and the problem with microfilms is that in many cases it is extremely difficult to observe with the naked eye, and a magnifying glass (loupe) is used. Is finally observed using. In the field of micro photography, recorded images are magnified 40 times or more for observation, so, for example, even in the case of minute uneven density,
Not only the quality of the finished image is deteriorated, but also in a fatal case, the recorded information is lost, which is a very serious problem in terms of the commercial value of the microfilm and the comb film.

The fine image density unevenness found in the above-described microfilm and comb film after development and drying has been known for a long time in the art,
The mechanism of its occurrence is not yet fully understood. It is believed that fine water droplets produced after washing with water during development processing cause drying irregularities when rapidly dried at high temperature, causing migration of image silver particles.

Fine image density unevenness that occurs after development and drying of the microfilm and comb film has been called a water mark or a water spot for a long time, and management of the automatic processor is not sufficient. Even under severe conditions, the appearance of microfilms and comb films in which water marks or water spots are unlikely to occur or at all do not occur has been awaited.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having improved developability. That is, (1) it is to provide a photographic light-sensitive material having good wettability of a processing solution without causing contamination of the processing solution in the developing process. (2) It is to provide a photographic light-sensitive material which does not cause unevenness in color density which occurs in the perforation part of a 35 mm roll film. (3) To provide a silver halide photographic light-sensitive material that does not cause minute image density unevenness due to water droplet unevenness during washing and drying after development processing.

[0013]

These objects of the present invention are directed to a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, said silver halide emulsion layer or other photographic material. This was accomplished by including poly (N-acylethyleneimine) grafted polysiloxane in at least one of the constituent layers. The poly (N-acylethyleneimine) graft polysiloxane used in the present invention is not particularly limited, but the compound preferably used in the practice of the present invention is represented by the following general formula (I). General formula (I)

[0014]

[Chemical 1]

The preferred specific examples of the compounds used in the present invention are shown below, but the present invention is not limited to these compounds.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

It has been found that when the poly (N-acetylethyleneimine) graft polysiloxane used in the present invention is added to a hydrophilic organic colloid coating solution and is applied at high speed, it can be applied uniformly without cissing or unevenness. The reason why the photographic light-sensitive material containing the compound used in the present invention is remarkably improved in the developability which is the object of the present invention is that the compound of the present invention has a polyamide bond similar to gelatin structure. It is estimated that the surface active behavior is due to the specific chemical structure having

The compound used in the present invention is used by adding it to the hydrophilic organic colloid coating liquid, and the amount thereof can be added in the range of 0.01 to 50 g per 1 kg of the coating liquid, but is preferable. Is suitably 0.05 to 5 g. As a method of addition, it is preferable to add it as a solution dissolved in water or a solvent that can be mixed with methanol or other water.

The above surface-active compound may be added to the coating liquid of any photographic layer constituting the photographic light-sensitive material, regardless of whether the layer is a photosensitive layer or a non-photosensitive layer. ..

In the light-sensitive material of the present invention, the addition of the compound of the above general formula forms a very uniform hydrophilic colloid coating film at low speed as well as at high speed coating. That is, uneven coating, comet and cissing of the coating film do not occur.

Gelatin is advantageously used as the hydrophilic organic colloid in the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
A wide variety of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers can be used.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin, photographic society journal, Japan (Bull.
Soc. Sci. Phot. Japan.) No. 16, p. 30 (1966)
You may use the enzyme-processed gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

The hydrophilic organic colloid layer in the present invention is a photographic coating layer using the hydrophilic organic colloid as described above, particularly gelatin as a binder, and examples thereof include a silver halide emulsion layer, a surface protective layer and a filter layer. , An intermediate layer, an antihalation layer, an antistatic layer, an undercoat layer, a backing layer and the like.

Since the compound of the present invention has a high solubilizing power and a high surface activity, it is suitable for coating a hydrophilic organic colloid layer obtained by dissolving and dispersing a poorly water-soluble photographic additive in a high-boiling organic solvent. It is preferably used.

Various silver halides can be used in the silver halide emulsion layer according to the present invention. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver chloroiodobromide. Silver iodobromide containing 2 to 20 mol% silver iodide and silver chlorobromide containing 10 to 50 mol% silver bromide are preferred. Crystal form, crystal structure, grain size of silver halide grains,
There is no limitation on the particle size distribution and the like. The crystal of silver halide may be a normal crystal or a twin crystal, and may be any of a hexahedron, an octahedron and a tetrahedron. Research Disclosure 2
Tabular grains having a thickness of 0.5 micron or less, a diameter of at least 0.6 micron, and an average aspect ratio of 5 or more may be used, as described in 2534.

The crystal structure may be uniform, the inside and the outside may be different in composition, or may have a layered structure.
Further, silver halides having different compositions may be joined by epitaxial joining, or may be composed of a mixture of grains of various crystal forms. Further, the latent image is mainly formed on the surface of the grain, and may be formed inside.

The grain size of the silver halide may be fine grains of 0.1 micron or less or large grains having a projected area diameter of up to 3 microns, a monodisperse emulsion having a narrow distribution, or a wide distribution. It may be a dispersion emulsion. These silver halide grains can be produced by a known method commonly used in the art.

The above-mentioned silver halide emulsion can be sensitized by a conventional chemical sensitization, that is, a sulfuric acid sensitization method, a noble metal sensitization method, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can impart color sensitivity in a desired light-sensitive wavelength region by using a sensitizing dye. Examples of dyes that are advantageously used in the present invention include methine dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, and hemioxonol, and styryl dyes, and these can be used alone or in combination of two or more.

Examples of the poorly water-soluble photographic additives used in the present invention include oil-soluble color couplers, antioxidants used to prevent color fog or color mixture, and anti-fading agents (eg,
Alkylhydroquinones, alkylphenols, chromanes, coumarones, etc.), hardening agents, oil-soluble filter dyes, oil-soluble ultraviolet absorbers, DIR compounds (eg,
DIR hydroquinones, non-colored DIR compounds, etc.),
Developer, dye developer, DRR compound, DDR coupler,
Etc. can be mentioned.

The internal oil-soluble color couplers include benzoylacetanilide type, pivaloylacetanilide type, pyrazolone type, cyanoacetyl type, phenol type,
A naphthol compound can be used. Typical examples of these are U.S. Pat.
No. 94, No. 3582322, No. 3891445, No. 2600788, No. 3062653, No. 31147.
No. 6, No. 3519429, No. 3558319, No. 3
No. 615506, No. 3834908, No. 236992
No. 9, No. 2474293, No. 2895826, No. 3
No. 591383, No. 3227544, No. 379038
No. 4, etc.

The high-boiling organic solvent in the present invention includes
For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), Benzoic acid esters (eg, octyl benzoate), alkylamides (eg, diethyl, laurylamide) and the like can be mentioned.

In the hydrophilic colloid coating liquid of the present invention, other than the above, stabilizers, hardeners, dyes, matting agents, photosensitive silver halide grains, other surfactants, polymer latex, fluorescent whitening The agent may contain various additives useful for photographic light-sensitive materials. Among these, an anionic surfactant is particularly preferable as the other surfactant used in combination with the compound of the present invention.

Regarding the above-mentioned additives, Product Licensing Index, Vol. 92, pages 107-110 (December 1971), Research Disclosure 15162 (November 1976), 17643 (19).
December 1978).

When the hydrophilic organic colloid coating layer containing the compound of the present invention contains a silver halide emulsion layer, the coating layer has a water permeability relationship with the silver halide emulsion layer. Alternatively, it does not have to have a water-permeable relationship with silver halide as in the back layer.

The compound of the present invention may be contained in any coating layer, but when it is added to the uppermost layer or its adjacent layer, the effect of improving the processability is remarkable.

Synthesis Example The compound used in the present invention can be easily synthesized by reacting an active hydrogen-containing polysiloxane such as an alcoholic hydroxyl group or an aminoalkyl group with oxazoline. For example, the following alcoholic hydroxyl group-containing polysiloxane

[0040]

[Chemical 6]

After 9.3 g was dissolved in 20.0 ml of methyclo and 8.0 g of triethylamine was added, 9.2 g of methanesulfonyl chloride was added dropwise while keeping the reaction temperature at 10 ° C. or lower. After the dropping, the mixture was stirred overnight at room temperature (25 ° C to 30 ° C). The reaction solution was poured into 300 ml of ice water and chloroform 2 was added.
The extract is washed three times with 00 ml, washed twice with 200 ml of water, and the chloroform layer is dried over sodium sulfate and evaporated under reduced pressure. A viscous polysiloxane sulfonate ester product is obtained. 10.3 g of the sulfonated product of this polysiloxane and 8.5 g of 2-methyl-2-oxazoline were dissolved in 20 ml of acetonitrile and reacted at 90 ° C. for 5 hours in a nitrogen atmosphere. After cooling, the tosylate anion was removed with an anion exchange resin, and the reaction solution was evaporated under reduced pressure. The residue was washed with ether to obtain the desired poly (N-acetylethyleneimine) grafted polysiloxane. Further, the residual amount of 2-methyl-2-oxazoline in the reaction solution was measured by GLC, but it was not detected, and it was confirmed that 100% of 2-methyl-2-oxazoline was polymerized.

[0042]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

EXAMPLE 1 Instead of the compounds I- (1), I- (2) and I- (3) in the protective layer, the compound examples 1, 2 and 5 of the present invention were used, and in the back dye layer 1,3-bis (vinylsulfonyl) -2
Except for the addition of 56 mg / m ² of propanol, otherwise exactly the same test coating was prepared, treated in the same way and evaluated in the same manner as in the example of JP-A-3-156442.
Table 1 shows the relationship between the type / addition amount of the surfactant and the generation of water spots (all the surfactants were added to the protective layer).

[0044]

[Table 1]

As is clear from the above results, the samples to which the compound of the present invention has been added to some extent (10 mg or more) have different types of development processing (i. Negative development, ii. Reversal development, iii. Direct reversal development). ), Rapid processing at high temperature (43 ° C) with a deep tank automatic processor (development time 15
It was confirmed that the water spot did not occur at all even in the case of (seconds). At that time, the water spot was clearly generated remarkably with the compound of the present invention or with other comparative surfactants. This shows how effective the compounds of the present invention are in preventing the formation of water marks.

Example 2 Sample 101 was prepared according to the example of Japanese Patent Application No. 3-297682.
The compounds of the present invention were added in place of the surfactant and the silicone compound shown in Table 4 of the same example, and samples 102 to 105 including the comparative compound were prepared. Then, the same treatment and evaluation were performed and the results shown in Table 2 were obtained.

[0047]

[Table 2]

From the results of Table 2, Samples 104 and 10 of the present invention
It is clear that in No. 5, uneven coloring in the perforation portion during hanging development is small, and repelling of the correction liquid in retouch correction can be prevented.

[0049]

It was found that when the compound of the present invention was used, there was no contamination of the treatment liquid and no fog was generated in the perforation part of the 35 mm color reversal roll film.

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layer and other photographic constituent layers is poly ( A silver halide photographic light-sensitive material comprising an N-acylethyleneimine) grafted polysiloxane.