JP2979349B2 - Processing method of silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method of processing silver halide photographic <br/> materials.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is processed after exposure by processes such as color development, desilvering, washing, and stabilization. For color development processing, color developing solution, for desilvering processing, bleaching solution, fixing solution, bleach-fixing solution, for washing, tap water, well water, chemically or physically treated water or ion-exchanged water, distilled water, stable processing Are used respectively. On the other hand, black-and-white photographic materials are processed by black-and-white development, fixing, and washing with water instead of color development. The temperature of each processing solution is usually adjusted to 20 to 50 ° C., and color and black-and-white photographic materials are immersed in each of these processing solutions for processing.

In order to commercialize such processing of a photosensitive material, it is necessary to reduce the processing amount as much as possible in order to reduce cost and manual work, reduce pollution load, compact processing equipment, and further enhance commercial value. It is required to obtain stable and excellent processing performance with a liquid. In order to obtain stable processing performance, it is essential that the composition of the processing liquid is always kept within a certain range, and in order to obtain excellent performance, it is uniformly immersed in a sufficient amount of processing liquid. Need to be

Accordingly, in the commercial processing of color photographic light-sensitive materials, an automatic developing machine having a processing tank for storing a large amount of processing liquid is used as in a color developing station. In addition, the replenisher for correcting the fatigue of the processing solution is automatically replenished so that the composition of the stored processing solution always falls within a certain range. Such a continuous replenishment system achieves extremely good results when a large amount of color photographic light-sensitive material is processed daily within a certain range. However, because the system supplies replenishment in proportion to the processing amount of the color photographic light-sensitive material, when the processing amount of the color photographic light-sensitive material is relatively small, the consumption and accumulation of the liquid composition components based on the development processing are reduced. Concentration of the processing solution due to evaporation of water and component changes due to air oxidation and decomposition of the components of the processing solution exceeded, and it was not possible to maintain a processing solution composition within a certain range only by replenishment supply based on the processing area, and therefore stable and excellent Processing performance cannot be obtained.

Recently, there has been a demand for diversifying consumer preferences, a demand for immediate color printing, and a demand for color photographic processing as a side job. There is a rapid shift from centralized processing to distributed small-volume processing by minilabs, and further to small-volume and rapid processing. Especially in the idle processing, the shortcomings of the continuous replenishment system are becoming a serious problem. On the other hand, a similar tendency is observed in the processing of black-and-white photographic light-sensitive materials. In particular, in replenishment processing in small processing machines, and in non-replenishment replenishment processing in small rapid processing machines, the problem of continuous replenishment systems is the same as in color processing. It is becoming.

[0006]

In view of the above demand, the present applicant has proposed a simple photosensitive material processing method as described in Japanese Patent Application No. 2-119254. This method has an advantage that stable processing performance can be obtained even with a small amount of processing solution, and the processing apparatus is downsized. However, when the photosensitive material was processed by the above method, fine spot-like processing unevenness was observed on the surface of the photosensitive material, which may be due to the influence of bubbles generated when the processing liquid was supplied between the photosensitive materials. confirmed. When the processing liquid is supplied between the photosensitive materials, the generation of bubbles is inevitable. If the generated bubbles remain between the photosensitive materials, the entire surface of the photosensitive material cannot be uniformly contacted with the processing liquid. turn into.
Such processing unevenness is particularly noticeable in the development processing. An object of the present invention is to solve the above problems,
And to provide a processing method of a silver halide photographic material with no treatment unevenness due to the influence of bubbles.

[0007]

The above objects of the present invention are attained by the following (1) to (3) . (1) At least one silver halide emulsion on a support
Silver halide photographic light-sensitive material having a layer
Either by the emboss provided or by the spacer with the convex part
By intervening, at least at the time of wet processing
Are overlapped so as to form a gap through which the photosensitive material can pass.
Back side (opposite side of emulsion layer side) or spacer
The space, which faces the emulsion layer surface of the light-sensitive material.
The contact angle of the surface of the substrate to the processing solution is 50 ° or less.
The folded photographic material is fixed and both ends are external.
Load into the processing vessel communicating with the tank and pump
Put the processing solution from the tank parallel to the surface of the photosensitive material in the processing container.
Or periodically reverses the direction after sending
Wherein the photographic material is processed
A processing method for silver photographic light-sensitive materials.

(2) Backing of silver halide photographic material
2. The silver halide photographic printing according to claim 1, which has a soluble layer on the surface.
Processing method of true photosensitive material.

(3) The silver halide photographic feeling of the spacer
Optical material having a soluble layer on the side opposite to the emulsion layer side
Item 6. A method for processing a silver halide photographic light-sensitive material according to item 1.

[0010]

[0011]

Hereinafter, the present invention will be described in detail. The present invention prevents the above-described processing unevenness from occurring by the following means. The first means is that the contact angle between the photosensitive material and / or the spacer and the processing liquid (for example, a developing solution) is 50 ° or less, preferably 40 ° or less. Even if bubbles are generated when the processing liquid is introduced, the bubbles move without stagnation between the photosensitive materials.
The contact angle of the photosensitive material is particularly important for the contact angle with the processing solution that comes into contact first.For example, the contact angle with the black-and-white developer for a black-and-white photosensitive material, and the contact angle with the color developer for a color photosensitive material. The contact angle is 50 ° or less, preferably 40 ° or less.

As a second means, by providing a soluble layer on the photosensitive material and / or the spacer, the soluble layer components are eluted into the processing solution when the processing solution is introduced between the photosensitive materials. Even if bubbles are generated when the processing liquid is supplied, the bubbles move with the elution of the soluble component and do not stay on the photosensitive material.

Therefore, the emulsion surface of the light-sensitive material can be brought into uniform contact with the processing solution, and good processing without unevenness can be performed. The contact angle between the silver halide photographic light-sensitive material and the processing solution is described in JP-A-2-271352. According to the description of the publication, the contact angle between the photosensitive material and the developing solution is 20 ° or less, so that even in the developing solution supply system in which the fatigue deterioration of the developing solution is reduced, even if the photosensitive material having a large size is developed, No development unevenness occurs. However, the processing method described in this publication is different from the method of the present invention in which a gap is formed between superposed photosensitive materials and a processing solution is introduced into the gap, so that the bubbles do not stay in contact with the emulsion surface and remain without bubbles. Since there is no adverse effect of the present invention, it is considered that there is no connection with the present invention.

In the present invention, the contact angle θ between the surface of the photographic material or the surface of the processing spacer and the processing solution can be determined by a conventional method. The details are obtained, for example, as follows.

As shown in FIG. 9, when a droplet of the processing liquid is placed on the surface of the photosensitive material or the spacer, ｒ of the bottom of the droplet immediately after that is denoted by r, and the height of the droplet is denoted by h, tan θ ₁ can be computed as h / r, it can be determined as a contact angle theta = 2 [theta] _1. The measurement of the contact angle can use a commercially available measuring device, for example, FACE manufactured by Kyowa Interface Science Co., Ltd.
An automatic contact angle meter CA-Z type can be used.

The contact angle is measured immediately after the treatment liquid is dropped on the surface of the photosensitive material or the spacer. The contact angle is defined as immediately after 2 seconds after dropping.
° or less, preferably 40 ° or less. Further, the contact angle is measured after the photosensitive material or the spacer after drying is stored at room temperature and normal humidity (for example, 20 ° C., 55% RH) for 30 minutes.

When a processing solution is dropped onto the surface of a photosensitive material or a spacer, the droplet generally tends to spread over time (decrease the contact angle), and it is preferable that this tendency is large. For example, the change in the contact angle between 2 seconds and 10 seconds after the treatment liquid is dropped is preferably 3 ° or more, particularly preferably 5 ° or more. Further, even a photosensitive material or a spacer having a contact angle of 50 ° or more immediately after dropping can be used as long as the contact angle decreases with time as described above. At this time, the decrease in the contact angle is preferably such that the change in the contact angle is 3 ° or more between 2 seconds and 10 seconds after the treatment liquid is dropped as described above,
In particular, it is preferably at least 5 °.

In the present invention, the surface of the photosensitive material is defined as the photosensitive material.
Say the back side of the fee. The surface of the spacer means a surface facing the emulsion surface of the photosensitive material. Further, it is preferable that the processing solution used for measuring the contact angle is evaluated by a processing solution (for example, a developing solution) with which the photosensitive material first comes into contact.
This is one important point in evaluating foam prevention. At this time, the processing liquid may be a new liquid, may be used in some cases, or may be a mixed liquid of both.

In the present invention, in order to reduce the contact angle between the surface of the photosensitive material or the spacer and the processing solution to 50 ° or less and to reduce the contact angle with the passage of time, for example, gelatin or the like is added to the surface of the photosensitive material or the spacer. By providing a hydrophilic colloid layer comprising a water-soluble polymer of the formula (1). Gelatin may be hardened by a hardener,
You don't have to. When providing a soluble layer, it is preferable not to harden.

In the present invention, as described above, it is preferable to provide a soluble layer on the back surface of the support of the photosensitive material or on the side of the spacer facing the emulsion surface of the photosensitive material. A hydrophilic polymer can be used.

The water-soluble polymer used for the above purpose in the present invention includes starches, mannans, seaweeds such as galactan and sodium alginate, plant mucous substances such as tragacanth gum, arabic gum and dextran, proteins such as gelatin and casein, and methylcellulose. And celluloses such as hydroxycellulose and carboxymethylcellulose, and synthetic polymers such as polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyvinylpyrrolidone, and polyacrylamide.
Among them, gelatin is particularly preferably used. These water-soluble polymers are used alone, but two or more kinds of polymers can be used as a mixture.

Gelatin can be used as a general-purpose lime-processed gelatin, as well as an acid-processed gelatin or a journal of the Japan Science Photographic Society (Bull. So
c. Sci. Photo. Japan) No. 16,30
Enzyme-treated gelatin as described on page (1966) may be used, and hydrolysates thereof may also be used. In addition, these gelatins are ion-exchanged,
Gelatin in which the type and amount of ions contained are controlled is also preferably used. For example, those in which calcium ions are exchanged for sodium ions or hydrogen ions using a cation exchange resin, those in which anions such as chloride ions are converted to hydroxyl ions by an anion exchange resin, or those in which these are combined are generally used. It is a target. So-called derivatized gelatin in which another group is bonded to gelatin is also preferably used. As the derivatized gelatin, phthalated gelatin, gelatin grafted with polyacrylamide, and the like are preferable. Further, a polymer in which an amino acid alkyl ester is amide-bonded to a gelatin decomposition product as described in JP-A 1-166032 can also be used.

It is also a useful method to use various surfactants when applying the hydrophilic substance. As the surfactant, any of anionic, cationic, amphoteric, nonionic and the like can be used, but anionic and nonionic surfactants are preferable, and anionic surfactant is particularly preferable. For example, Deliyagin, "Film Coating Theory"
(BM Deraygin, SM Levi: Fi
lm CoatingTheory: The Foca
l Press, 1964), p. 159 to p. 164, and surfactants described in Ken-ichi Eda, "Surfactant Research-2, Application to the Photographic Industry" (Koshobo, 1963) and the like are preferably used. These are typical examples, and a commercially available surfactant can be added. A commercially available surfactant is Det.
ergents & Emulsifiers (McC
utcheon's Publication / Ann
ua)).

The above-mentioned processing of the present invention may be carried out successively in all the processing steps of the photographic light-sensitive material, but it may be applied to only some of the steps and the other steps may be carried out by a conventional processing method. In the present invention, the gap formed when the photosensitive materials are overlapped,
It can be formed by providing projections periodically or randomly on a portion of the silver halide photosensitive material other than the image surface, preferably on the edge of the photosensitive material. In addition, for example, a non-photosensitive film having a convex portion (eg, a sheet or a long shape), a film having an uneven surface (eg, a sheet or a long shape), and a gap formed by supporting both edges of the photosensitive material A spacer such as a member to be used can be used.

The photosensitive material may be wound in a roll shape and overlapped, or may be overlapped in a plane. In the present invention, the method of superimposing in the form of a roll is particularly preferable in that the development processing (photographic processing) can be performed in a very compact container. The gap between the light-sensitive materials in the present invention may be within a range where the processing solution can be stably supplied, and is preferably in a range of 0.1 mm.
It is from 0.1 to 2 mm, more preferably from 0.05 to 2 mm, particularly preferably from 0.05 to 0.5 mm. The narrower gap is preferable in terms of making the container to be processed compact, etc. However, if it is too narrow, on the contrary, it is not preferable in that a problem such as unevenness during development processing occurs and it becomes difficult to obtain a good image. .

In order to form the gap, there are a first method in which a convex portion is provided on both ear sides of one side of the photosensitive material, and a second method in which a spacer is arranged between the photosensitive materials. The first method includes a method of embossing both ears (both ends) of the photosensitive material by pressure, heating, and the like, and a method of forming a corrugation. Specifically, knurls used in the Japanese style can be used. The shape of the emboss is triangular pyramid, pyramid such as quadrangular pyramid, cone,
It may be a polygonal pillar such as a triangular pillar or a cylinder. Size is diameter (D)
0.01 to 2 mm, height (H) is 0.01 to 2 m
m, the emboss interval (L) is 40 cos ⁻¹ [(20−
H) / 20] mm (0.0)
1 ≦ H (mm) ≦ 2, and H / 5 ≦ D (mm) ≦ 15H is more preferable.

As a method of forming a corrugation, both ends of the film may be corrugated by heating and pressing. The height of the wave may be the same or twice as high as the height (H) of the emboss. The wave gap may be the same or twice as large as the emboss gap (L). The size may be the same or twice as large as the emboss interval (L).
In the second method, a dummy film having convex portions on both sides (only at both ends) and a photosensitive material are superimposed on each other and spirally wound to form a gap, and a gap is formed along both ends of the photosensitive material. Alternatively, a spacer capable of supplying the processing liquid may be provided. The method of forming the protrusions of the dummy film is the same as the method of forming the protrusions provided on the photosensitive material, and the size of the protrusions may be 2 to 4 times the size of the protrusions of the photosensitive material (provided that the protrusions are formed on both surfaces). There is).

In order to supply the processing liquid between the photographic materials, the processing liquid is supplied, for example, by a pump or the like using a pressure or a reduced pressure or a combination of the two. The pressure at this time varies depending on the viscosity of the processing liquid in the gap formed in contact with the photosensitive surface of the photosensitive material, but is usually 0.2 to 20 kg / cm ² , preferably 1 to ²⁰ kg / cm ² .
6 kg / cm ² . In the present invention, it is preferable that at least an equal amount of the processing liquid is replaced by the gap volume before one step of the processing is completed. The gap capacity is the sum of the capacities of gaps formed in contact with the photosensitive surface of the photosensitive material. In the processing of a black-and-white photographic light-sensitive material, one step of processing is a development step, a fixing step, a stop step, a stabilization step, a washing step, and the like. In the processing of a color photographic light-sensitive material, a color development step, a fixing step , Bleaching step, bleach-fixing step, reversing step, stabilizing step, washing step and the like. It is not necessary to replace the processing solution by an equal amount or more in all of these processes, but it is preferable that at least one process including the developing step is replaced by an equal amount or more.

The replacement of the treatment liquid is preferably at least one equivalent, more preferably from 1 to 100 equivalents, more preferably from 1 to 10 equivalents. Here, when the replacement is performed by changing the flow of the processing liquid, it is preferable to change the processing liquid two or more times for one processing step, more preferably 3 to 100 times.
Particularly preferably, it is changed 4 to 10 times. Thereby, a more stable and uniform photographic image can be obtained. Here, the gap capacity varies depending on the length of the photosensitive material to be used, in addition to the width of the photosensitive material. For example, in the case of 24 to 36 sheets of photosensitive material having a width of 35 mm, 5 to 30 ml, preferably 7 to 15 m is used.
By setting it to 1, it is possible to perform a good developing process while being compact. The amount of the treatment liquid can be preferably 5 to 50 ml, more preferably 10 to 30 ml.

Further, in the processing method of the present invention, since the amount of the processing solution is small due to its compactness, even if it is disposable, there is no particular problem such as contamination. In addition, since it is not necessary to consider a temporal change (deterioration) during the processing of the processing liquid, it becomes easier to design the processing agent. When the processing solution is replaced, the method is not particularly limited. For example, when a long photosensitive material is spirally wound, it is necessary to supply the processing solution in a direction substantially perpendicular to the longitudinal direction. It is preferable from the point of view. Here, the substantially perpendicular direction is preferably within ± 30 °. Even in the case of a sheet-shaped photosensitive material, it is preferable to move the processing liquid in the direction in which the path length of the gap is short from the viewpoint of processing properties (such as suppression of uneven development).

Further, the replacement direction of the processing liquid may be kept constant during one step of the processing, or may be changed with time (for example, the reverse direction). The replacement direction of the processing solution is
It is preferable to change over time from the viewpoint of processing uniformity. By forcibly supplying the processing liquid to the narrow gap by the supply means instead of free fall or the like, unexpectedly good photographic images could be obtained even with a small amount of the processing liquid. By placing the photosensitive material in the flow of the processing liquid, the processing can be performed extremely efficiently. This is presumably because advanced liquid agitation, which could not be obtained by the conventional tank developing method, became possible. According to the present invention, in the processing step, it is possible to supply and flow a small amount of the processing liquid without substantially moving the charged photosensitive material into the processing container, thereby enabling efficient processing. According to the present invention, there is an effect that development processing can be performed with a processing liquid amount at least twice as large as a gap volume in contact with a photosensitive surface of a photosensitive material. Here, not substantially moving means that the photosensitive material inside is not moved within the container by manually shaking the container.

Further, when carrying out on the device that automates the process does not require Ru create a main liquid flow by greatly vibrating the processing vessel. ADVANTAGE OF THE INVENTION According to this invention, processing can be started using a fresh processing liquid and can be fully used. This means not only efficient use of the processing solution, that is, reduction of the amount of the processing solution, but also stabilization of the processing, and also in addition to the case where the processing solution is the developing solution, to increase the sensitivity of the photosensitive material and reduce the size of the image. It was also found that they also had a remarkably excellent effect. In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. The average grain size of the silver halide grains in the photographic emulsion (grain diameter for spherical or near-spherical grains,
The ridge length is defined as the particle size and is expressed as an average based on the projected area). The particle size distribution may be narrow or wide. The silver halide grains in the photographic emulsion layer may have a regular crystal form such as cubic or octahedral, or may have an irregular shape such as spherical or tabular.
lar) or a compound of these crystal forms. It may consist of a mixture of particles of different crystal forms. The silver halide grains may have different phases between the inside and the surface layer or may consist of a uniform phase. Further, the particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle.

The photographic emulsion used in the present invention is Chimie et Physique Photographique by P. Glafkides.
) [Paul Montel, 1967
Year], Photographic Emulsion Chemistry (Phot) by GF Duffin
ographic Emulsion Chemistry) [The Focal Press, 1966], Vier
Making and Coating Photographic Emulsion by VL Zelikman et al
[The Focal Press, 19
64 years] and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good.

In the course of silver halide grain formation or physical ripening, cadmium salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof,
An iron salt or its complex salt may coexist. For chemical sensitization, for example, H. Friese
r) Hen Die Grundlagender Photographischen Prozesse mit
Silber-halogeniden) [Akademische Verlagsgesellschaf
t), 1968] The method described on pages 675 to 734 can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines);
Reduction sensitization using a reducing substance (for example, stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); periodicity of noble metal compounds (for example, gold complex salts, Pt, Ir, Pd, etc.) Metal sensitization using a complex salt of a metal of Table VIII) or the like can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy substitution (1,3,3)
Add benzenethiosulfonate, benzene sulfinic acid, known as antifoggants or stabilizers such as base Nzensurufon acid amides, many compounds; 3a, 7) tetraazaindenes) and penta-aza indene be able to.

As a binder used in the photographic emulsion layer or other hydrophilic colloid layer, gelatin is advantageously used, 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole sugar Can be.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxabrin nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzene An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a rhodanine nucleus, or a thiobarbituric acid nucleus. A 5-6 membered heterocyclic nucleus can be applied. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosur.
e) It is described in J, Vol. 176, 17643 (issued in December 1978), page 23, IV.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, an aromatic one in a color development process.
It may contain a compound capable of forming a color by oxidative coupling with a primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative). For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides,
Pivaloylacetoanilides), and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion.

Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor during development (a so-called DIR coupler) may be used. In addition to the DIR coupler, a colorless DIR coupling compound which is colorless and releases a development inhibitor may be contained. Known methods for introducing couplers into silver halide emulsion layers, such as U.S. Pat.
The method described in 2,322,027 is used. For example, alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate), phosphates (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate), citrates (such as tributyl acetyl citrate), Benzoic acid esters (eg, octyl benzoate), alkyl amides (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (eg, tributyl trimesate), and the like, or having a boiling point of about Organic solvents at 30 ° C. to 150 ° C., for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β Ethoxyethyl acetate, was dissolved in methyl cellosolve acetate, etc., they are dispersed in a hydrophilic colloid. The above-mentioned high-boiling organic solvent and low-boiling organic solvent may be mixed and used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) Active vinyl compounds (1,3,3)
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-triazine etc.), mucohalogen Acids (mucochloric acid, mucofenoxycyclolic acid, etc.) and the like can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, acceleration of development, contrast enhancement, enhancement) Various surfactants may be included for various purposes such as feeling. Various other additives may be used in the silver halide photographic emulsion of the present invention. Examples of the additive include a whitening agent, a dye, a spectral sensitizer, a desensitizer, a hardener, a coating aid, an antistatic agent, a plasticizer, a sliding agent, a matting agent, a development accelerator, an oil, and a mordant. , An ultraviolet absorber, an anti-fading agent, an anti-fog agent and the like can be used. As these additives, those described in RESEARCH DISCLISURE 176, pages 22 to 31 (RD-17643) (Dec., 1978) can be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material or stabilizing photographic performance. . In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film or paper commonly used for the photographic light-sensitive material or a synthetic support. Useful as flexible supports are films, semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (Eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like, which is coated or laminated. In the photographic light-sensitive material of the present invention, a photographic emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various known coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like can be used. U.S. Pat.Nos. 2,681,294, 2,761,791,
The method described in 3,526,528 is an advantageous method.

The present invention is also applicable to multilayer multicolor natural color photographic materials having at least two different spectral sensitivities on a support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as needed. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler.
In some cases, different combinations can be used.

Further, the photographic light-sensitive material used in the present invention includes various color and black-and-white light-sensitive materials. For example, color negative films for photography (general use, movies, etc.), color reversal films (slides, movies, etc., sometimes without couplers), color photographic paper, color positive films (movies, etc.) , Color reversal photographic paper, color photosensitive material using silver dye bleaching method, photographic photosensitive material for plate making (lith film, scanner film, etc.), X-ray photographic photosensitive material (direct / indirect medical use, industrial use, etc.), black / white for photography Negative films, black and white photographic paper, photosensitive materials for micros (for COMs, microfilms, etc.) can be mentioned. Among them, photosensitive materials for photography,
In particular, the method of the present invention is effective for color photographic materials for photography.

When the light-sensitive material used in the present invention is a color light-sensitive material, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 28 μm or less, and the film swelling speed T1 / 2 Is preferably 30 seconds or less. The film thickness is preferably 25 μm or less, and T1 / 2 is preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (two days), and the film swelling rate T1 / 2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Phot) by A. Green et al.
og. Sci. Eng.), Vol. 19, No. 2, p. 124-129, and can be measured by using a swellometer (swelling meter) of the type described above. 90% of the maximum swelling film thickness reached when treated for 15 minutes
Is defined as the time required to reach the film thickness.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness. In the photographic processing of the light-sensitive material of the present invention, any of known methods can be used, and a known processing solution can be used. The processing temperature is usually selected between 18 ° C. and 50 ° C., but may be lower than 18 ° C. or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied. The method of the present invention may be used for all of these treatment steps, or may be used for one or more steps.

Known black and white developers include known dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), and aminophenols (eg, N-methyl-p-aminophenol). The developing agents can be used alone or in combination. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent,
A p-phenylenediamine compound is preferably used,
As representative examples, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonic acid Salts. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution comprises a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids,
Triethylenediamine (1,4-diazabicyclo [2,
Various preservatives such as 2,2] octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers , A fogging agent such as sodium boron hydride, an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, and a phosphonocarboxylic acid. Various chelating agents such as, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethrillo-N, N,
N-trimethylene phosphonic acid, ethylenediamine-N,
N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black-and-white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. "Photographic Processing Chemistry" by LFA Mason, Focal Press (1966)
266-229, U.S. Patent Nos. 2,193,015 and 2,592,
No. 364 and JP-A-48-64933 may be used.

The developing solution may further include a pH buffer such as a sulfite, a carbonate, a borate and a phosphate of an alkali metal, a development inhibitor such as a bromide, an iodide and an organic antifoggant, or an antifoggant. Agents and the like. If necessary, water softeners, preservatives such as hydroxylamine, benzyl alcohol, organic solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; polycarboxylic acid-based chelating agents described in U.S. Pat. No. 4,083,723;
S) It may contain an antioxidant described in 2,622,950.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Bleaching agents such as iron (III), cobalt
Compounds of polyvalent metals such as (III), chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used.
Typical bleaching agents are ferricyanide; dichromate; organic complexes of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetate iron (III) complex salt and persulfate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Furthermore, aminopolycarboxylate iron (II
I) Complex salts are particularly useful in both bleaching and bleach-fixing solutions. These aminopolycarboxylic acid iron (III)
The pH of the bleaching solution or bleach-fixing solution using the complex salt is usually 5.5 to 8
However, it is also possible to treat at a lower pH for faster treatment.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812.
Compounds having a mercapto group or a disulfide bond described in JP-A-53-95,630 and Research Disclosure No. 17,129 (July 1978);
Thiazolidine derivatives as described in No. 140,129; thiourea derivatives as described in U.S. Pat. No. 3,706,561;
No. 6,235, iodide salts; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compounds, thioureas, and a large amount of iodide, but thiosulfate is generally used, and ammonium thiosulfate is most widely used. Can be used for As a preservative of the bleach-fixing solution, a sulfite, a bisulfite, a sulfinic acid or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
evisionEngineers) Vol. 64, pp. 248-253 (5 May 1955)
Month) can be obtained.

According to the multi-stage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and benzotriazoles, etc. It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

Washing water in processing the light-sensitive material of the present invention
The pH is between 4 and 9, preferably between 5 and 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally, it is 20 to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, JP-A-57-8,543, JP-A-58-14,834, JP-A-60-220,
All known methods described in No. 345 can be used. Further, after the water washing treatment, a stabilization treatment may be further performed. As an example, a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photography, can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. US Patent No.
Indoaniline compounds described in No. 3,342,597, No. 3,3
No. 42,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat.No. 3,719,492, urethane compounds described in JP-A-53-135,628 Can be mentioned. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds and JP-A-56-64339, 57
Nos. 144,547 and 58-115,438. The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually a temperature of 33 ° C to 38 ° C is standard,
A higher temperature promotes the processing to shorten the processing time, and a lower temperature can improve the image quality and the stability of the processing solution.

[0059]

An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited only to this embodiment. 1 is a plan view of the photosensitive material 2 on which embossing has been performed, FIG. 2 is a cross-sectional view of the photosensitive material 2 along a longitudinal direction, and FIG. 3 is a cross-sectional view of the photosensitive material 2 wound in a roll. is there. The photosensitive material 2 is obtained by cutting a color negative film into a width of 35 mm and a length of 1 m. Embosses 6 are formed along the longitudinal direction outside the image forming areas 4 at both ends in the width direction. The perforations are not shown. The emboss 6 can be easily formed by, for example, a knurl (a rotary embossing tool used in Japanese style). By forming the emboss 6 on the photosensitive material 2, the emboss 6 of the photosensitive material 2 protrudes from the emulsion surface or the surface on the opposite side (support surface). When the photosensitive material 2 is wound into a roll as shown in FIG. 3, the top of the emboss 6 contacts the overlapping portion, and a gap is formed between the overlapping photosensitive materials 2. On the support surface of the photosensitive material 2,
A soluble layer of gelatin or the like for reducing the contact angle with the processing solution is provided.

FIG. 4 is a plan view of the embossed spacer 8, FIG. 5 is a cross-sectional view of the spacer 8 along the longitudinal direction, and FIG. 6 is a diagram in which the spacer 8 and the photosensitive material 2 are superposed and wound into a roll. It is sectional drawing of the turned state. As shown in FIG. 6, when the spacer 8 and the photosensitive material 2 are overlapped and wound in a roll shape, a gap is formed between the overlapping photosensitive materials 2. It is formed.
A soluble layer of gelatin or the like is coated on at least the front and back surfaces of the spacer 8 opposite to the emulsion surface in order to reduce the contact angle with the processing solution.

FIG. 7 is a partially cutaway perspective view of a photosensitive material processing container, into which the embossed photosensitive material 2 shown in FIG. 1 is loaded. A shaft 14 is provided inside the processing container 12, and the photosensitive material 2 after the exposure is wound with the leading end fixed to the shaft 14, and a gap is formed between the photosensitive materials 2. The shaft 14 is provided with a frame 16 so that the photosensitive material 2 does not move. Further, couplers 18 can be mounted on the upper and lower sides of the processing container 12,
Various processing liquids are supplied into the processing container via the coupler 18. The processing container 12 can be built in the camera, also serving as a patrone. In addition, even if the photosensitive material 2 does not have the emboss 6, the photosensitive material 2 and the spacer 8 can be overlapped and wound around the shaft 14 as shown in FIG. Further, the processing container 12 shown in FIG. 7 has a configuration in which the long photosensitive material 2 is wound and accommodated, but the processing container 12 is configured to accommodate the sheet-shaped photosensitive material in an overlapping manner while forming a gap. You may.

FIG. 8 is a block diagram of the processing apparatus. The processing vessel 12 is connected to a processing apparatus by a coupler 18.
For example, five types of processing liquid tanks 28 are prepared, and each processing liquid is separately supplied to the processing container 12 by the pump 29 to process the photosensitive material 2. First, the first processing liquid is supplied to the processing vessel 1
2. When supplied to the flow path constituted by the pump 20, the switching valve 22, and the drain cock 24, the switching valve 22 forms a closed flow path. Then, predetermined processing of the photosensitive material 2 is performed by circulating the processing liquid in the closed channel by the pump 20. Here, by periodically reversing the direction of liquid supply by the pump 20, the processing liquid spreads well around the emboss 6 formed on the photosensitive material 2, and no processing unevenness occurs near the emboss 6. . When the processing with the first processing liquid is completed, the drain cock 24 is opened, and at the same time, the air intake 26 of the switching valve 22 is opened, and the processing liquid in the processing container 12 is discharged out of the closed flow path by natural inflow of air. Is done. Next, the second, third, fourth, and fifth processing solutions and the fifth processing solution are similarly supplied into the processing container 12, and the photosensitive material 2 is processed.

When the processing with all the processing solutions is completed, the processing container 12 is connected to the coupler 18 of the drying unit 30. In the drying unit 30, the air dehumidified by the dehumidifier 32 is supplied to the processing container 12 by the blower 34 through the heater 36 and the duct 38, and the photosensitive material 2 in the processing container 12 is dried.

[0064]

[Embodiment 1] Preparation of Embossed Spacer The base used for the spacer was processed into the following six types. (1) Untreated surface TAC base (cast by a conventional method and not subjected to surface treatment such as undercoating) (2) Gelatin undercoating (unhardened film, thickness of undercoating 0.5 μm)
m) TAC base (3) Gelatin undercoat (hardened with formalin, undercoat thickness 0.5 μm) TAC base (4) Surface-untreated PET base (cast by an ordinary method and not subjected to surface treatment such as undercoat) (5) Gelatin undercoat (unhardened, undercoat thickness 0.5μ)
m) PET base (6) Gelatin undercoat (hardened with formalin, undercoat thickness 0.5 μm) The shape of the PET base spacer is about 120 μm thick and 35 mm wide, and the emboss position is 3 m from both ends in the width direction of the film.
m, the shape of the emboss is conical, the height is 250 μm, and the diameter at half the height is 600 μm. Embossing conditions: As shown in FIG. 5, embosses having projections 10, 10 on the upper and lower surfaces of a base 8 were provided by knurling (rotary embossing tool used in Japanese style).

2. Film used (1) Super HG100 manufactured by Fuji Photo Film Co., Ltd. (2) Super HG400 manufactured by Fuji Photo Film Co., Ltd. (3) Gold100 manufactured by Eastman Kodak (4) Gold400 manufactured by Konica Corporation (5) Super DD200 manufactured by Konica Corporation (6) Super DD400 manufactured by Konica Corporation (All of these are trade names)

3. The above-mentioned six types of embossed spacers and six types of films are combined and co-wound with the embossed protrusions on the emulsion side of the film so that the gap between the weight films is 230 μm in the processing container shown in FIG. The container was accommodated, and the processing shown in the following step was performed using the processing liquid shown below in the processing apparatus shown in FIG. In this case, 1 in the container shown in FIG.
The treatment was performed while moving the solution up and down about 20 ml once every 5 seconds. Table 1 shows the results.

Step Processing time Processing temperature Color development 3 minutes and 15 seconds 38 ° C. Bleaching 1 minute 38 ° C. Bleaching and fixing 3 minutes and 15 seconds 38 ° C. Washing 1 minute and 40 seconds 35 ° C. Stable 40 seconds 35 ° C. The composition of the treated solution was as follows.

(Color developing solution) (g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxyamine 2.4 4- (N- Ethyl-N-β-hydroxyethylamino) 4.5-2-methylaniline sulfate 1 liter by adding water, pH 10.00

(Bleaching solution) (g) Ammonium bromide 100 Ferric ammonium salt of ethylenediaminetetraacetic acid 120 Disodium salt of ethylenediaminetetraacetic acid 10.0 Ammonium nitrate 10.0 The following bleaching accelerator 2.0 (H ₃ C) ₂ N— (CH ₂ ) ₂ -SS- (CH ₂ ) ₂ -N (CH ₃ ) ₂ ammonia water 17.0 ml 1 liter of water was added, pH 6.5

(Bleach-fixing solution) (g) Ammonium bromide 50.0 Ferric ammonium salt of ethylenediaminetetraacetic acid 50.0 Disodium salt of ethylenediaminetetraacetic acid 5.0 Ammonium nitrate 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240 ml Ammonia water 10.0 ml In addition, 1 liter pH 7.3

(Stabilizing solution) (g) Formalin (37% w / v) 2.0 ml Polyoxyethylene-p-monononyl 0.3 phenyl ether (average degree of polymerization 10) 1 liter by adding water Rinse water: tap water of the following water quality water. pH 7.1 Calcium ion 23mg / l Magnesium ion 8mg / l

[0072]

[Table 1]

As is apparent from the results shown in Table 1, TA
In the case of using a spacer hardened by coating gelatin on C or PET, development unevenness considered to be due to bubbles occurred only in a small part, and it can be considered that almost satisfactory processing was performed. When gelatin is coated on TAC or PET and an unhardened spacer is used, development unevenness considered to be due to bubbles does not occur at all, and it can be considered that good processing has been performed. The spacer (1) is undercoated with the following composition to form a spacer (7)
It was created. Undercoat is a matting agent of diacetyl cellulose, polyoxyethylene dioctadecyl ether phosphate, polyester resin, polyacrylonitrile in methyl ethyl ketone solvent (average particle size about 2 μm)
Was added to the spacer (1) at 1 μm (spacer thickness: about 120 μm, width: 35 mm) and embossed at the same time.

For 2 seconds, 10 seconds, and 30 seconds of the spacer (3),
The contact angles with the processing solution after 44 seconds are 44 °, 39 ° and 3 °.
6 °. Also, the spacer (7) has 2 seconds, 10 seconds,
The contact angles with the treatment liquid after 0 seconds were 40 °, 40 °, and 39 °, and the results of performing the same treatment as described above using these spacers are shown in Table 2.

[0075]

[Table 2]

From the results shown in Table 2, when the contact angle is 50 ° or less, the foam unevenness was improved. In addition, when a spacer was used such that the contact angle decreased with the passage of time, the foam unevenness was further improved.

Example 2 Films (1) and (2) used in Example 1 (the contact angle with the processing solution after 2 seconds were 44 ° for film (1) and 44 ° for film (2)) as well as the spacer. Was embossed, and gelatin was applied to the back surface of the film (the surface opposite to the emulsion surface) in the same manner as in the case of the spacer to harden the film. Each of these films was wound without using a spacer (the gap between the films in this case was 230 μm), and processed in the same manner as in Example 1 according to the above-described processing steps. As a comparative example, a film not coated with gelatin on the back surface of the film was prepared and treated similarly. As a result, the film coated with gelatin on the back surface does not generate any development unevenness, which is considered to be due to bubbles, and can be regarded as having been subjected to good processing.

Example 3 An aqueous solution of polyvinyl alcohol (molecular weight: 30,000) was applied to a thickness of 1 μm as a soluble layer on the back surface of the film (1) of Example 1 (film thickness: about 120 μm, width: 35 mm). After embossing was provided in the same manner as in Example 2, development processing was performed in the same manner as in Example 1. As a result, no unevenness due to bubbles occurred.

Example 4 The same soluble layer and embossing as in Example 3 were provided on one side of the spacer (1) of Example 1, and the same processing as in Example 1 was performed.
As a result, no unevenness due to bubbles occurred.

[0080]

According to the present invention, the contact angle of the photosensitive material and / or the spacer with the processing liquid is 50 ° or less, so that the processing liquid is introduced between the superposed photosensitive materials with a gap. Even when bubbles are generated, the bubbles move without staying between the photosensitive materials. Further, by providing a soluble layer on the photosensitive material and / or the spacer, the soluble layer component is eluted into the processing solution when the processing solution is flowed between the photosensitive materials, so that bubbles are generated when the processing solution is supplied. However, the bubbles move with the elution of the soluble component and do not stay on the photosensitive material. Therefore, the emulsion surface of the light-sensitive material can be in uniform contact with the processing solution, and good processing without unevenness can be performed.

[Brief description of the drawings]

FIG. 1 is a plan view of a photosensitive material.

FIG. 2 is a sectional view of a photosensitive material.

FIG. 3 is a sectional view of a photosensitive material wound in a roll shape.

FIG. 4 is a plan view of a spacer.

FIG. 5 is a sectional view of a spacer.

FIG. 6 is a cross-sectional view of a state in which a spacer and a photosensitive material are stacked and wound.

FIG. 7 is a partially cutaway perspective view of a photosensitive material processing container.

FIG. 8 is a configuration diagram of a processing apparatus.

FIG. 9 is an explanatory diagram showing a contact angle with a processing liquid.

[Explanation of symbols]

 2 Photosensitive Material 4 Image Area 6 Emboss 8 Spacer 10 Convex 12 Processing Container 14 Shaft 16 Frame 18 Coupler 20 Pump 22 Switching Valve 24 Drain Cock 26 Air Inlet 28 Processing Liquid Tank 29 Pump 30 Drying Unit 32 Dehumidifier 34 Blower 36 Heater 38 duct

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Sasaki 210 Nakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. (56) Reference JP-A-2-271352 (JP, A) JP-A-62-56951 (JP, A) JP-A-49-78548 (JP, A) JP-A-49-54432 (JP, U) JP-B-55-37742 (JP, B2)

Claims (3)

(57) [Claims] 1. The method according to claim 1 , wherein at least one layer of silver halide is provided on a support.
A silver halide photographic light-sensitive material having an emulsion layer,
By embossing provided on the material
Intervening at least during wet processing.
Superposed so as to form a gap through which the solution can pass,
The back side of the material (the side opposite to the emulsion layer side) or the spacer
When interposed, the stripe facing the emulsion layer surface of the photosensitive material is used.
The contact angle of the surface of the pacer with the processing liquid is 50 ° or less.
The superimposed photosensitive material is fixed and both ends are outside.
Into the processing vessel that communicates with the
Process liquid from the tank onto the surface of the photosensitive material in the processing container.
Feed liquid in the line direction, or periodically change the
Inverting and processing the photographic material.
A method for processing a silver halide photographic material. 2. The method according to claim 1, wherein the back surface of the photographic material is silver halide.
2. The silver halide photographic light-sensitive material according to claim 1, which has a soluble layer.
How to handle fees. 3. A silver halide photographic material for a spacer.
2. The method according to claim 1, wherein a soluble layer is provided on the side opposite to the emulsion layer side.
For processing silver halide photographic light-sensitive materials.