JPS63235940A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain the excellent finishing quality of a sensitive material by using the photosensitive material provided with an emulsion layer for the titled method, and said emulsion layer contains 4-40mol% of silver iodide in the core of a silver halide particle, and is composed from a silver bromide, a silver chlorobromide or a silver chloride, and also contains the silver iodide lower than that contd. in the core or does not containing the silver iodide, in the one layer - the plural layers of the outer shell of said particle. CONSTITUTION:The photosensitive material provided with the emulsion layer is used in the titled method of using the photosensitive material provided with the emulsion layer on a supporting body, and said emulsion layer contains 4-40mol% of the silver iodide in the core of the silver halide particle, and is composed from the silver bromide, the silver chlorobromide or the silver chloride, and also contains the silver iodide less than that contd. in the core, or does not contain the silver iodide, in the one layer - the plural layers of the outer shell of said particle. And, the photosensitive surface of the photosensitive material comes into contact with the stream of a processing solution, without substantially exposing said surface to a free air, in at least one step of developing and processing steps of said material. Thus, the excellent image quality is easily obtd. with stable and relatively rapid.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming method that can stably, relatively quickly and easily produce excellent image quality. This invention relates to an image forming method using a stream.

(Prior art) Conventionally, the development process for silver halide light-sensitive materials, even for black-and-white light-sensitive materials, did not require a fixing and stabilizing bath or water washing process after development, but color light-sensitive materials were generally more complicated and longer than black-and-white light-sensitive materials. Processing time is required. That is, after color development, a desilvering treatment step and a water washing bath or stabilizing bath are performed. Before color development, prebath or first bath in case of color reversal development.
Black and white development is not provided, and the desilvering process often consists of bleaching, bleach-fixing or fixing the reduced silver. Development processing in the instant photography method uses a silver salt or dye diffusion transfer method, in which an image-receiving layer and a group of photosensitive layers are separated in advance, a positive image is formed directly on the image-receiving layer by development, and then a positive image is formed directly on the image-receiving layer. The photosensitive layer group is peeled off or separated, and only the resulting image can be observed, thereby speeding up the development process.

Development processing is usually carried out by immersing the photosensitive material in a processing solution placed in each storage tank at a predetermined temperature, time, and agitation conditions, or using a slit or pot to apply a viscous developer. A method of spreading or coating on the photoresist surface of the material and developing it;
There is a method of developing by contacting a processing liquid with a normal viscosity in a spray-like manner or in a film-like manner. In addition, automatic developing devices include hanging type developing machines, roller conveyance developing machines, cine automatic developing machines, rotary developing machines such as automatic developing machines for disk films, rotating drum type developing machines, and reel-wound developing machines. There is. In addition, ITek's venturi processing, jet spray processing, and recorder processing, such as U.S. Patent No. 2! The developing machine and P described in Goto No. 22 etc.
SdE magazine number! Volume, page 92 to page S< (79 the 7th year)
A processing machine described in is known.

Immersion development processing of photosensitive materials is widely used as a method that can achieve uniform and stable finishing quality. However, the number of storage tanks is large, and the amount of processing liquid, replenisher liquid, and drainage liquid is large, making it easy to use a relatively large developing machine. With the spread of photosensitive materials, the demand for high finishing quality has become stronger. For this reason, substances that inhibit the development of images, especially micro images, and promote imagewise development have begun to be widely used in photosensitive materials, particularly color photosensitive materials, and in high concentrations. Examples include silver halide grains containing a high content of silver iodide, especially silver halide grains with a multilayer structure, DIR compounds, DAR compounds, etc. Although high image quality can be obtained using these compounds, there are drawbacks such as deterioration in uniformity of finishing quality and delay in development processing.

Development processing using a viscous developer has difficulties in removing the viscous processing solution after processing and in making each development process continuous. The method of developing by contacting in a spray-like or film-like manner tends to cause fatigue of the processing solution, especially the developer, and has problems in making the processing continuous and stable.

Particularly, in color developing laboratories, immersion development is often performed, which is suitable for processing large quantities of color photosensitive materials. Therefore, when the amount of photosensitive material to be processed suddenly decreases or during slow processing, increase the amount of processing replenisher to 5 times the normal amount, and add a recovery solution such as Fuji Film's "Repaiving Solution". They spend a lot of time and effort trying to restore performance.

In an image forming method using a photosensitive material comprising a silver halide photosensitive layer provided on a support, the cores of the silver halide grains contain y mole to gθ mole percent of silver iodide; Using a photosensitive material in which the outer shell has seven or more emulsion layers consisting of silver bromide, silver chlorobromide, or silver chloride containing less or no silver iodide than the core, ■Development processing is performed. An image characterized in that in at least seven steps of the process, the photosensitive surface of the photosensitive material is in contact with a stream of a processing solution without being exposed to substantially free air. Formation method.

Regarding the development processing of color negative photosensitive materials, the color development processing time is longer than that of color photographic paper, and it is said to be extremely difficult to maintain high sensitivity and high finish quality with the same quick and simple processing as color photographic paper. It is required that the color development processing time be at least 2 minutes or less (excluding drying time).

A seventh object of the present invention is to provide an image forming method that can stably achieve excellent finishing quality with a small replenishment amount of processing liquid. Second, by providing a development processing method that can be processed quickly and easily even when using a silver halide emulsion with a relatively high amount of silver iodide and a high concentration of a development inhibitor to obtain excellent finishing quality. be. Other objects will be apparent from the description of the invention.

The present inventors studied various photosensitive materials and their development methods, and found that the object of the present invention can be achieved by using the following image forming method.

A first feature of the present invention is the use of a system that includes development processing using a processing liquid stream. Development processing using a processing liquid stream refers to ``development processing in which a flow of processing liquid created to have a flow rate different from the transport speed of the photosensitive film is brought into contact with the photosensitive film of the photosensitive material in a limited space.'' In order to smoothly carry out continuous rapid processing, the photosensitive material is preferably processed while being continuously conveyed in a limited space. The direction of the process liquid stream is
- In order to start the process with a new processing solution and to reduce the amount of the processing solution, it is preferable that the direction is the same as the direction in which the photosensitive material is transported. The flow rate of the processing liquid stream is different from the transport rate of the sensitive material to be processed, and the relative speed is preferably controlled to create substantially turbulent rather than laminar flow. This allows extremely even, stable and efficient processing. The processing liquid stream may be isolated from free air in order to keep the processing liquid capacity stable and require only a small amount.

Here, the limited space referred to in the developing process using a processing liquid stream means a developing machine that is cut off from free air, and is a developing machine that satisfies the shaded area shown in FIG.

Therefore, conventionally known laminar flow development has a large interface with air and is outside the scope of the automatic processor of the present invention.

As the term suggests, laminar flow development is a development process in which a processing stream flows gently over a photosensitive material as a laminar flow due to the force of gravity, and is completely different from the development process using a processing liquid stream as used in the present invention.

That is, in this process, as described above, the sensitive material moves between the narrow syslits, and the processing liquid is supplied at a speed different from the movement, so that processing is performed in a substantially turbulent state.

FIG. 7 shows the relationship between tank liquid capacity and tank opening degree for commercially available general processors, special processors such as minilabs, and processors of the present invention.

In the figure, A, B, C, and D are commercially available general processors, E, and F.
indicates a special processor such as a minilab, and Y indicates a processor used in the embodiments -/and - of the present invention.

In Y, the tank liquid capacity is extremely small, and in the case of Y, the opening degree is extremely small. Here, the degree of aperture refers to the degree of aperture, since development using a processing solution stream in the present invention often starts with the newly supplied processing solution, excluding the stabilizing bath and rinsing bath. Processing proceeds stably and efficiently while maintaining the performance of the supplied processing liquid, and processing time is shortened. By reducing the cross-sectional area of the limited space and controlling the relative transport speed of the processing liquid stream and the photosensitive material in accordance with the processing time, extremely efficient processing can be achieved, and not only the amount of drainage but also the recovery It is possible to reduce the amount of liquid and brightening liquid.

Furthermore, even when intermittent processing, that is, continuous processing is interrupted and very small amounts of light-sensitive material are processed intermittently, it is possible to easily obtain stable finishing quality.

In addition, since the treated liquid can be collected continuously in a trench, the treated liquid can be regenerated efficiently.

Therefore, by applying the image forming method using a processing liquid stream according to the present invention particularly to color development processing, a compact, quick and simple color development processing system can be created.

In treatment with a treatment liquid stream, the surface of the member creating the confined space may be provided with a treatment liquid impregnated polymeric sheet material which is preferably movable. It is convenient for removing scum from the processing liquid and stably supplying the processing liquid in small quantities.

The second feature of the present invention is the photosensitive material, particularly the photosensitive silver halide grains used therein. In a photosensitive silver halide emulsion, the silver iodide component provides crystal lattice defects to increase photosensitivity, and in particular provides trapping centers for holes generated by exposure, and is particularly effective in expanding the spectral sensitivity wavelength range. Not only is this advantageous, but it also has many advantages in the developing process, such as improving graininess and improving image sharpness due to inter-image effects. All photographic photosensitive materials use silver halide grains containing silver iodide. On the other hand, as mentioned above, silver iodide has many drawbacks, such as slowing down the progress of development, suppressing the desilvering action, and making the finishing quality unstable during continuous processing. The silver halide grains used in the present invention have a multilayer structure consisting of a core and seven or more shell layers. In other words, the core has a high concentration of
Silver bromide, silver chlorobromide containing less than or less than the silver iodide content of the core with seven or more layers in its outer shell with a silver iodide content of more than mol% to θ mol % - / θ - It is equipped with silver chloride. Advantageous properties such as high sensitivity, sensitivity stability, image sharpness and graininess are contributed by the high silver iodide content in the core, and by reducing the silver iodide content in the outer shell, the disadvantages of silver iodide can be overcome. Efforts are being made to reduce this. For example, it reduces the delay in initial development, improves the deterioration of graininess caused by delayed development, stabilizes gradation reproduction, and expands gradation development latitude. However, this alone does not eliminate the defects of silver iodide.

In particular, the color photosensitive material used in the present invention has a silver halide photosensitive layer (BL) containing a yellow coupler, a silver halide photosensitive layer (GL) containing a magenta coupler, and a cyan photosensitive layer on a support. A silver halide photosensitive layer (RL) containing a coupler is provided, and silver halide grains are present in at least seven photosensitive layers of about 100 to 100 g.
A silver halide emulsion having a multiple structure including a core containing preferably 30 molar silver iodide and a shell containing silver iodide at a lower content than the core is used. For example, JP-A Akiotsu θ-/G333/ issue, Akiotsu 0-/3t!
'33 and No. 4/-, No. 5757, 2/-
It can be manufactured by the method described in 2y, No. 239, 滝昭igo/-2ta Otsu 7g No. 7, Tokugan Shoni/-233370, and Tokugan Sho 6/-2/Go♂j. can.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention. Preferred silver halide is silver iodobromide containing silver iodide having an average halogen composition of less than θ molar ratio. Particularly preferred is silver iodobromide containing silver iodide in an average halogenated composition ranging from 0.2 to 20 mole percent. In addition, in order to achieve both high sensitivity and high image quality, it is necessary to use the Tokukai Shoto θ-/2? As described in Guku No. 3, it is preferable that the average silver iodide content of silver norogenide in all the emulsion layers be below the molar coefficient. It is known that increasing the average silver iodide content of silver halide significantly improves graininess and helps improve fog stability and microimage sharpness, but if the silver iodide content exceeds a certain level, This results in drawbacks such as slow development speed, desilvering, and slow fixing speed.

This drawback is that the layer (ADL) that adsorbs and removes iodide ions, development inhibitors, or desilvering action inhibitors generated at the end of the development process or in the desilvering process is an intermediate layer of the photosensitive material, and an antihalation agent. , can be reduced or eliminated by providing it in a protective layer or backing layer. For example, Tokko Aki?
-3737, Tokukai Sho! To O-! No. 230, Japanese Patent Application Publication No. 1986/
-31.3g! No., U.S. Patent No. 37'1r13 and patent application No. 0-/! It is preferable to use the hydrophilic colloid layer described in No. t910d etc. as the ADL.

It is also preferred that the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention have a core silver iodide content of at least 7 layer mols and at most 6 mols. The silver iodide content of the shell is preferably 5 molar or less.

The core may contain silver iodide uniformly, or may have a multilayer structure consisting of phases having different silver iodide contents.

Further, the silver halide emulsion layer used in the present invention uses silver halide grains whose core or shell has been chemically sensitized, and the total amount of metal impurities other than gold and iridium contained in the grains is 3 ppm or less. It is preferable to contain silver halide grains, and by using such a silver halide emulsion, a highly sensitive silver halide photographic material can be obtained.

A method for preparing a silver halide emulsion having a significantly low content of metal impurities (other than gold and iridium) contained in silver halide grains as described above includes water, which is an essential raw material for preparing a silver halide emulsion. Hydrophilic colloids such as gelatin, soluble silver salts such as silver nitrate, KBr, KQ! , K.I.
In addition to purifying soluble alkali halides such as , NaBr, and NaCl to remove metal impurities from the raw materials, it also eliminates the contamination of metal impurities from the reaction vessel during the preparation of silver halide emulsions. This can be achieved by appropriately combining techniques such as preventing or adjusting reaction temperature and reaction conditions.

−／　gu　− The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubic or hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Preferred tabular or columnar silver halide grains according to the present invention have a diameter/thickness ratio (asbestos ratio) of more than 100 g, for example, those having a diameter exceeding t and those having a diameter of 100 g to 100 g.

Generally, tabular silver halide grains are tabular or columnar with two parallel faces, and therefore have the above-mentioned "thickness".
is expressed as the distance between λ parallel planes constituting a tabular silver halogenide grain.

For example, when silver iodobromide is used as the tabular silver iodobromide grain with a multilayer structure according to the present invention, the silver iodobromide tabular grain has a layered structure consisting of a plurality of phases each having a different iodide content. You can also use something. Tokukai Akira! ♂−
//3ri2za issue or tokukaisho! Preferred examples of the halogen composition of tabular silver halide grains and the intragrain distribution of halogen are described in Data No. 9y33 and the like.

In general, the desirable relationship between the relative iodide contents of each phase of tabular silver halide grains is determined by the details of the development process (for example, developer (contained in)・Amount of silver halogenide solvent)
It is desirable to select the most suitable one.

Tabular silver halide grains include, for example, bonded silver halide crystals in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, and epitaxially grown silver halide crystals (such as silver bromide crystals). Silver chloride, silver iodobromide,
A crystal obtained by epitaxially growing silver iodide, etc. with chloride, or a crystal obtained by epitaxially growing silver chloride, silver bromide, silver iodide, silver chloroiodobromide on hexagonal or regular octahedral silver iodide), etc. . Examples of these are U.S. Pat. No. 41,413! .

No. 507, same, ri 13. Or! ``This is exemplified in No. 7, etc.

Tabular grains are described by Gutoff, Photographic Science and Engineering.
tographic 5science and engineering
US Pat. No. 4133, 0
Guza No., same Gu, Gu 39. ! Ko θ and British Patent No. U
, //2, No. 167, etc.

A monodispersed emulsion has an average particle diameter (7) of about 0. A silver halide emulsion having a grain diameter standard deviation S of 0.20 or less. Generally, the silver halide emulsion used in the present invention can be produced by a known method, for example, Research Disclosure, Volume 77, A/7
413 (July 2, 1997J') 2.22~. Page 23, °゛1. Emulsion Preparation
ation and Types)” and the same, /za2
It is possible to follow the method described in Vol.

-77 - As the silver halide emulsion used in the present invention, the published technical report? , 6-939. Silver halide grains having a crystal face defined by Miller index (nn/) (n≧2, n is a natural number) on the outer surface as described in No. r are preferably used.

Also preferably used is a silver halide emulsion having a hollow conductive portion from the surface toward the inside, as described in JP-A-7.3-337.

Silver halogenide emulsions having such a large specific surface area are more effective when used in combination with the present invention, especially when color sensitized, because they are easier to achieve sensitivity than emulsions of the same volume.

A more preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention has a diffraction angle (-!θ) of 3t to Goo! β of Cu in the range of 0
When the curve of diffraction intensity versus diffraction angle of the (2coθ) plane of silver halide is obtained using a line, there are two diffraction maxima: a diffraction peak corresponding to the core portion and a peak corresponding to the shell portion.
There are seven local minima between them, and the diffraction corresponding to the core part -/? - Particles having a structure such that the strength is ///, θ~3// of that of the shell part. Particularly preferably, the diffraction intensity ratio is //! ~3//, and furthermore, //3~3//.

This type of double or multilayer structure makes it possible to use high-iodine silver iodobromide emulsions without slowing down the development speed, and achieves photosensitive materials with excellent graininess even with a small amount of coated silver. can do.

The average grain size of the silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains).

In the case of cubic particles, the principal is the particle size, and the projected area is also expressed as an average. ) is not particularly important, but 0.0!
The thickness is preferably 10 μm or more.

When a layer having the same color sensitivity is composed of two or more emulsion layers, the average size of silver halogenide grains in each emulsion layer having the highest sensitivity is preferably from 0.11 μm to 0.0 μm, and preferably from 0.1 μm to 0.0 μm. More preferably, the thickness is 2 μm or more and 2.5 μm or less.

These tabular silver halide grains can also be used by monodispersing the grain size and/or thickness of the silver halide grains, as described in Japanese Patent Publication No. 2-/73 and Otsu. It is.

Regarding the ratio of tabular silver halide grains in the emulsion containing tabular silver halide grains used in this technology, to the total projected area, ! It is preferable that the θ coefficient is greater than or equal to 2θ, more preferably the 2θ fission or greater, and particularly preferably the θ coefficient or greater.

Also, Tokukai Showa J7-/, 33j Ri No. 0, the same! ? -/θ?
! , No. 2 or the same! Tar/Otsu, 2! Composite particles in which silver salts having different compositions are epitaxially grown on host particles as described in No. 0 can be preferably used in the present invention. Such particles are preferable as means for realizing the present invention because they exhibit photographic properties with high sensitivity and high contrast.

In addition, Unexamined Japanese Patent Publication No. 10-7
Silver halide emulsions grown in the presence of tetrazaindene, such as those described in No. 2co-23o, have a high silver iodide content and excellent monodispersity, so they exhibit high sensitivity and excellent graininess. Therefore, it is preferably used as a silver halide emulsion for use in the present invention.

Also, Tokukai Akira! And one 72g! - As shown in the number,
Silver halide emulsions which have been subjected to total sulfur sensitization or gold selenium sensitization in the presence of a nitrogen-containing heterocyclic compound are preferably used as silver halide emulsions for use in the present invention because they exhibit low capri and high sensitivity.

Also, Tokukai Shoj Tar/Lid 3rd No. 5 or the same Tower/
The slightly rounded cubic or/hedral crystals described in Kuta No. 3 Kugu are preferred as the silver chloride emulsion used in the present invention because they provide high sensitivity performance.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be allowed to coexist.

Among these, silver halide emulsions whose grains are formed in the presence of iridium have high sensitivity (Japanese Patent Publication No. 3-Geta 3j, Japanese Patent Publication No. 3,273,!h).

No.) is particularly preferred as the silver halide emulsion used in the present invention.

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chirnie et Physique Pho
tographique (published by Paul Monte1, 1979), G, F.

Photographic Emuls by Duffin
ionChemistry (The Focal
Published by Press, / Rig Otsunen), V, L, Zelikm
Making and Coati by an et al.
ng Photographic Emulsion (
It can be adjusted using the method described in The Focal Press, 1967). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method of reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

Silver halide emulsions are usually chemically sensitized as core grains or shelled grains. For chemical sensitization, see for example "DieGrundlag" edited by H. Frleser.
ender Photography Pro
zesse mit Silver-halogeni
den” (Akademische Verlagsg
esellchaft.

/rigg,r)t7s-73g pages can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization method using noble metal compounds (e.g., total complex salts, p
t, Ir.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Pd can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with methine dyes or the like during the silver halide grain formation process, or before or after chemical sensitization, if necessary. The 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.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be included in the emulsion. For example, aminostyl compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat.
．． 2/) are particularly useful.

In the present invention, in particular, patent application Sho tO-/, 2.27J-9
Open-/. A silver halide emulsion supersensitized with a compound represented by the following general formula (I) is preferred.

General formula (1) (wherein R represents an aliphatic group, aromatic group or heterocyclic group substituted with at least 7 -COOM, -803M or hydroxyl groups, M is a hydrogen atom, an alkali metal atom, (Represents quaternary ammonium or quaternary phosphonium.) Specific examples of the compound represented by the general formula (I) can be found in Japanese Patent Application No. Sho J/-jθ/7jt, page 3 to Shiri 1, 2j.
- Described on page 7.

In Patent Application Sho/-/90/, No. 29, etc., it is stated that the sharpness of the image and the stability of the image forming surface are improved by reducing the thickness of the film on the support to about /μ to /μ. has been done. Further, the light-sensitive material according to the present invention using the multi-structured silver halide emulsion of the present invention has a protective layer of O,Sμ to 3μ, and has a dry film thickness on the support excluding the protective layer of /jμ to 3μ.
By providing a hydrophilic colloid film containing a photosensitive layer with a thickness of 0 μm, particularly preferably 1 μm to 2 μm, the physical strength can be increased to prevent scratches on the photosensitive film.

Preferably, each photosensitive layer is thin, and the intermediate layer is thick.

As the binding agent or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin (treated with lime or acid), but other hydrophilic colloids may also be used. Can be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Example 1. f
, active halogen compounds (such as,2,y-dichloro-6-hydroxy-/,!,!-)riazine) and active vinyl compounds (such as /,3-bisvinylsulfonyl-2-propatur, /,λ-bisvinyl) Sulfonylacetamidoethane (such as a vinyl polymer having a vinylsulfonyl group in a side chain) is preferred because it quickly hardens hydrophilic colloids such as gelatin and provides stable photographic properties.

In particular, it is preferable to use a hardening agent containing more vinylsulfonyl groups than moss. Further preferred are compounds represented by the following general formula (I[). By using this, it is possible to improve the runnability in the developing machine that performs the development process using the stream of the present invention, and to provide strong physical properties such as scratches.

General formula (It) In the formula, R1 and R2 are the same or different hydrogen, a hydroxy group, or a substituted or unsubstituted alkyl group, such as methyl, ethyl, isopropyl group, or hydroxyethyl group, and Z is a bond or a covalent group, such as Oxygen, which is a nonmetallic atom,
Indicates a sulfur atom, a substituted or unsubstituted divalent amine group, etc. n and m are the same or different/or not! is an integer. Specifically, Examples/Examples of the specification of Tokko Sho 7-2G 2J'9, synthesis examples of Tokko Sho Ku-13363, and Tokko Sho! Examples of the compounds of No. 7-2 No. 90.2 include the compounds shown above.

Furthermore, in order to improve runnability in the developing machine and improve image sharpness, the present invention includes a hydrophilic polymer latex with an average particle diameter of 0.0/μ to O1jμ, as shown below. It is preferably contained in the sex colloid layer.

(a) has a coupler residue capable of coupling with an oxidized product of an aromatic-grade amine developer to form a dye, and has at least 7
containing a dispersion of polymeric couplers derived from monomeric couplers having polymerizable ethylene groups.

(b) Contains a dispersion of a color coupler dispersed in coexistence with a water-insoluble, organic solvent-soluble polymer.

(c) Vinyl polymer latex particles are still inorganic particles, especially for the protective layer, θ, 0/μ or μ, especially O0θ/μ or /μ, and large particles of -μ to 5μ are mixed. good.

It is to contain a dispersion of a so-called "polymer color coupler. For example, the polymer coupler described in JP-A-Kokai Shoj. Targ, 2!g. 3, etc. is used.

The polymer coupler used in the present invention has the following general formula CI
At least seven monomeric couplers derived from the monomeric coupler represented by [1] and which do not have the ability to oxidatively couple with a polymer having a repeating unit represented by the general formula [■] or an aromatic-grade amine developer. It is a copolymer with seven or more types of non-chromogenic monomers containing ethylene groups. Here, one or more monomeric couplers may be simultaneously polymerized.

-Kota- General formula [■] General formula [■] In the formula, R is a hydrogen atom, a lower alkyl group having a carbon number / -
represents a chlorine atom, and X is -CONH-5-NHC
ONH-1-NHCOO-1-COO-1-SO2-1
-CO-2-S 02 NH-1-NH8O2-1-O
CO-1-0CONH-5-NH-1-NHCO-1-
8- or -〇-, Y is -CONH- or -CO
It represents O-, and A represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 7 to 70 carbon atoms, and the alkylene group may be linear or branched.

Q is a cyan color-forming coupler residue capable of coupling with the oxidized product of an aromatic-grade amine developer to form a dye;
Represents a magenta color-forming coupler residue or a yellow color-forming coupler residue.

represents m, n and 1lFio or/, but m, n and l are never O at the same time.

Here, the substituents of the alkylene group, aralkylene group, or arylene group represented by A include an aryl group, a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, a sulfonamido group, Sulfamoyl group, halogen atom, carboxy group, carbamoyl group, alkoxycarbonyl group,
Examples include sulfonyl groups. When there are λ or more substituents, they may be the same or different.

Among the color coupler residues represented by Q, the cyan color forming coupler residues are preferably phenol type [v] or naphthol type [■].

H In the formula, R3 is an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an atom, an alkoxycarbamoyl group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an arylcarbamoyl group. group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, or an arylureido group, and when there are two or more substituents, they may be the same or different.

p is an integer between θ~3 and q is an integer between θ~g.

Zo represents a hydrogen atom, a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, even if these groups are substituted. often,
Examples of substituents include aryl group, nitro group, hydroxyl group, cyan group, sulfo group, alkoxy group, aryloxy group,
Examples include acyloxy group, acylamino group, alkylsulfonamide group, alkylsulfamoyl group, halogen atom, carboxy group, alkylcarbamoyl group, alkoxycarbonyl group, alkylsulfonyl group, and alkylthio group. When there are two or more of these substituents, they may be the same or different.

The magenta color-forming coupler residue is preferably a pyrazolone, indashilon type, or pyrazoloazole type, for example, in formula 33, R4 is 11 birazoline! - represents a well-known type of substituent in the 7-position of the on coupler, e.g. an alkyl group,
Substituted alkyl group, aryl group or substituted aryl group [Substituted groups include halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, and cyan group. ]
represents.

Z2 represents a leaving group bonded to the coupling position with a hydrogen atom, oxygen atom, nitrogen atom or sulfur atom, and Z2
is bonded to the coupling position with an oxygen atom, nitrogen atom or sulfur atom, these atoms are an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group or a heterocyclic group. f) (herein, the alkyl group, aryl group, and heterocyclic group may have a group represented as a substituent for the aryl group in R4), and further in the case of a nitrogen atom, also means a group containing the nitrogen atom that can form an S-membered or a membered ring to serve as a leaving group (for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, etc.).

-3da- Yellow color forming coupler residues include acylacetanilide type, especially pivaloylacetanilide type [■]
, benzoylacetanilide type [] , alkoxycarbonyl group, norogen atom, alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group, cyan group, thiocyano group, etc.
These substituents may be the same or different.

z3 is a hydrogen atom or the following general formula [XI], [X
■] or [X■] represents a group.

oR9[X] R9 represents an optionally substituted aryl group or heterocyclic group.

R10% ” 11 are each hydrogen atom, halogen atom, carboxylic acid ester group, amine group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted It represents a phenyl group or a heterocycle, and these groups may be the same or different.

Wl represents a nonmetallic atom required to form a Ky-membered term, a j-membered ring, or a g-membered ring with OY NYO in the formula.

Among the general formulas [XIV], preferred are [X■] to [8U].

In the formula, R12 and R13 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, and R14, R15, and -3 and -R16 each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. or an acyl group, W2 represents an oxygen or sulfur atom.

The pyrazoloazole type, which is a magenta color-forming coupler residue, includes the following: For example, the general formula WLXMIla,
Among the compounds represented by Ml[b, XMl[c, XMI[d, XMl[e], R1, R2, Hll, R12, R
A compound in which any one of 13 is replaced with a bonding chain can be used as the residue.

General formula [■] M=external representation, R1 and R2 represent a hydrogen atom or a substituent, 1
. . . , X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer.

When Za=Zb is a carbon-carbon double bond, it may be a part of an aromatic ring, and R1, R2 or X may form a multimer of a double or more.

Among the pyrazoloazole magenta couplers represented by the general formula [X■a], preferable ones are the following general formula [X■a
], [X■b], [X■C], [X■d] and [xV
fAe].

Among couplers represented by general formulas [X■a] to [X■e], those preferred for the purpose of the present invention are general formulas [X■a] to [X■e], Bll, R1
2 and R13 may be the same or different and each represents a hydrogen atom, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterooxy group, an acyloxy group, or a carbamoyl group. Oxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkyl group / - thio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group , an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and particularly preferred are an alkyl group, an alkoxy group, and an alkylthio group. , aryl group, aryloxy group, arylthio group, acylamino group, and anilino group. X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom or sulfur atom and is decoupled. R11, R12, R13 or X may form a cibis form which is a divalent group.

It may also be in the form of a polymer cassillator in which the coupler residues represented by the general formulas [X■a] to [XMIe) are present in the main chain or side chain of the polymer, and in particular, vinyl monomers having a moiety represented by the general formula Preferably, the polymer derived from R11, R12, -g λ - R13,z or X represents a vinyl group or a linking group.

General formula CXWa), [X■b], [X■C], [X■d
] and (XMIe) is included in the vinyl monomer, the linking group represented by R11, R12, R13 or X is an alkylene group (a substituted or unsubstituted alkylene group, for example, methylene group, ethylene M
, /, 10-decylene group, -CH2CH20CH2CH
2-1 etc.), phenylene group (substituted or unsubstituted phenylene group, for example /14t-phenylene group, /, 3-
Phenylene group, -NHCO-1-CONH-1-〇-1
It includes groups formed by combining groups selected from -OCO- and aralkylene groups (for example, [E, etc.)].

Preferred linking groups include the following.

-NHCO-2-CH2CH2-1 -CH2CH2-0-C-2 I -CONH-CH2CH2NHCO-1-CH2CH2
0-CH2CH2-NHCO-3 The vinyl group may have substituents other than those represented by the general formulas CXMia] to [XVIe], and preferred substituents are hydrogen atoms, chlorine atoms, or lower carbon atoms Represents an alkyl group (eg, methyl group, ethyl group).

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (such as methacrylic acid), and In addition to esters or amides derived from these acrylic acids, methylenebisacrylamide, vinyl ester, acrylonitrile, methacrylonitrile, aromatic vinyl compounds, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether, maleic anhydride Examples include maleic acid, maleic ester, N-vinyl-pyrrolidone, N-vinylpyridine, and co- or gouvinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together.

For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methyl acrylate and diacetone acrylamide, etc.

As is well known in the polymeric color coupler art, the non-chromogenic ethylenically unsaturated monomers to be copolymerized with the solid water-insoluble monomeric coupler depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymeric couplers used in the invention are lipophilic and are preferably used in latex form.

As for a method of emulsifying and dispersing a lipophilic polymer coupler in an aqueous gelatin solution in the form of a rubber latex, the method described in U.S. Pat. This method is also applicable to the formation of homopolymers and copolymers.

Next, when dispersing the lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution, the organic solvent used to dissolve the lipophilic polymer coupler is
Alternatively (less preferably) it is removed during evaporation during drying of the applied dispersion. Methods for removing the solvent include those that are somewhat water soluble, such as those that can be removed by washing with water in a gelatin noodle mold, and those that are removed by spray drying, vacuum or steam purging.

In addition, examples of organic solvents that can be removed include esters such as lower alkyl esters, lower alkyl ethers, ketones,
halogenated hydrocarbons such as methylene chloride or trichloroethylene, fluorinated hydrocarbons, alcohols such as n
-butyl alcohol, n-octyl alcohol, and combinations thereof.

Any type of dispersant may be used to disperse the lipophilic polymer coupler, but ionic surfactants, particularly anionic surfactants, are preferred.

Amphoteric types such as C-cetylpentine, n-alkylaminopropionate, N-alkyliminodipropionate can also be used.

In addition, permanent solvents, i.e., high boiling point ( , :zoo 0 or more) of water-immiscible organic solvents may be added.

The proportion of the colored portion in the polymer coupler is normal! ~
Although 0% by weight is desirable, 20 to 70% by weight is particularly preferred in terms of color reproduction, color development and stability.

In this case, the equivalent molecular weight (grams of polymer containing 1 mole of monomeric coupler) is about 2jθ to yoθ01, preferably about 2jθ to 10θ0, and even about 2! θ to 6θθ, but is not limited to this.

The coating amount of the polymer coupler of the present application is 2 x 10-3 mol per 1 mol of silver in terms of color forming unit! ×/θ−
1 mole, preferably /x/θ-2 or more! ×10-” mole.

With the polymer coupler of the present invention, sufficient diffusion resistance can be achieved with a low equivalent molecular weight, and the amount of high-boiling organic solvents used in combination can be reduced. Also, polymer couplers are 0.0/~o
, rμ, it is possible to reduce the deterioration of the physical strength of the coating film.

Examples of polymerization initiators suitable for making the polymeric couplers of the invention can be found in various publications, such as J. Magn.
,2), ,203~/θ,/973.

Co11ect, Czech, Chem, Com
mun,, 4t, 2(z),,:z39ri~ri0
0, /977.

JP-A-741-/2! , 3/7, Tokukai Sho 7//L
! ? 17 Dog, Zh, Org, Khim,, 7 (/ /), ss
t 3~7°/97/.

Co11ect,Czech,Chem,Comm,,
33.

//, zr (/p, <).

J, Am, Chem, Soc,, trr, /p/z
(/96g).

seen in These objects of the invention are based on the following general formula CXI
This was achieved by using a latex of a polymer coupler polymerized with a polymerization initiator represented by X:].

General formula [X■] In the formula, R1 is the number of carbon atoms/~! R2 represents a straight or branched alkyl group having 7 to 20 carbon atoms.

For example, the following compound, jO- Specifically, JP-A-Sho! It is shown in the tags 2jf4t3 and so on.

Color couplers typically use a low boiling point organic solvent that can be removed before or during coating film formation and a high boiling point organic solvent that remains in the film. However, in the present invention, a water-insoluble, organic solvent-soluble polymer may be used instead for dispersion. Organic solvents with high boiling points reduce the scratch strength of the film and increase the bulk of the coated film, making it undesirable for thinning the film. The polymer used in the present invention is, for example, a polymer described in Japanese Patent Publication No. 2003-3θ-Kutaku and the specification of the applicant's application filed on July 70, 1997, and is, for example, p-/polybutyl acrylate-. Acrylic acid polymer (♂,,
5': / p-2 polyacrylate-acrylic acid polymer (♂r
:/5) p-3 polybutyl acrylate-acetoacetoxyethyl methacrylate-acrylic acid polymer (ZB:/θ:
/ri) p-g polybutyl acrylate-N-cyanoacetyl N'-methacrylhydrazine polymer = (qo: /
θ) p-j Polymethyl methacrylate p- Poly N-tert-butyl methacrylamide p-7 Poly N-ethoxyethyl methacrylamide, etc.

The color coupler herein refers to a compound that can undergo a coupling reaction with an oxidized form of an aromatic primary amine developer.

Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) It is described in the patent cited in 1979.

The color coupler incorporated in the light-sensitive material has a ballast group or is made into a polymer so that it has diffusion resistance, and the molecular size is approximately 2! Preferably, the angle is 6θθ from O. A two-equivalent coupler substituted with a coupling-off group is more preferred than a four-equivalent coupler in which the coupling active position is a hydrogen atom. Further, a coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 21 θ
No. 7,270, same No. 2. And 7! , No. 0#7 and No. 31.2 Otsu, f, No. 306 of the same. The use of two-equivalent yellow couplers is preferred for the present invention, and is described in U.S. Pat. Kugu No. 7, 9.2♂, No. 3.
No. 933.307 and the same No. 933.307, θ2 approval.

The oxygen atom dissociative yellow coupler described in g, 2θ issue, etc. or Tokukosho! ? -/θ739, U.S. Patent No. G, Gθ/, No. 76.2, U.S. Patent No.
i, RD/zost (March 1979), British Patent No. 1. Ri2! , No. 020, West German Application Publication Tube 2. Co/Re, No. 977, No. 21.2, No. 3, No. 3, No. 3
．． 2ri! No. 17 and Co.

A typical example thereof is the nitrogen atom dissociative yellow coupler described in No. 33,272. α-pivaloylacetanilide-based couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide-based couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably j-pyrazolones and pyrazoloazoles such as pyrazolotriazoles. Examples include glue couplers. ! -Pyrazolone couplers are preferably those in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Patent No.
/,0#,! No., same No. ko.

3ri No. 3,703, same No. 2. Otsu θ0, 7F&” No. 2, riOza, f73, No. 3,0621g53, No. 3, /3;, 2, No. ♂99 and No. 3゜ri3A, 0/! It is written in the issue etc. Two pixels!
- As a leaving group for the pyrazolone coupler, the nitrogen atom leaving group described in US Pat. The arylthio group described in No. 977 is particularly preferred.

Also, European Patent No. 73. It has a ballast group as described in No. 3! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, US Patent No. 3.
Pyrazolobenzimidazoles as described in θ61,473.2, preferably US Pat. No. 3.72! , pyrazolo[r,/-c)[/,,2. Dacitriazoles, Research Disclosure +241
220 (Monday in /ri/y) and JP-A Showi θ-333!
Pyrazolotetrazoles and research described in No. 2
Disclosure 24t Ko 3θ (9 months ago) and Tokukai Showa θ-3G! Examples include the pyrazolopyrazoles described in No. 2. U.S. Patent No.
The imidazo[/,,2-b]pyrazoles described in U.S. Pat. Pyrazolo [y, sb:] [/ as described in No.

λ, ri]triazole is particularly preferred.

Polymer couplers are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol and phenol couplers, US Patent No. 4T74T.

No. 293, preferably the naphthol couplers described in U.S. Patent No. G, 0! ,2,. 2/2 issue, same issue.

Typical examples include two-pixel naphthol couplers of the oxygen atom dissociative type, which are described in No. 4,39A, No. 1.2, No. 233, and No. 1.29t, 20θ. Further, specific examples of phenolic couplers include U.S. Patent Nos. 2 and 3, U.S. Pat. Za9! , is written in issue 2z etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.00.
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus described in No. 2;
U.S. Patent No. 2, 77.2, No. 2, U.S. Patent No. 3,
7. tF, 30I! No. I>, No. G, /, 24.3
No. 9, No. 33, No. 077, No. 327゜773, West German Patent Publication No. 3.3.29,729, European Patent No. 12/3, No. 5, etc. 2, j
-Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. 41, No. 22, No. 333.99
No. 41, 1.1. ! ;/,! ! No. 2 and No. 27, No. 7, etc., which have a phenylureido group at the co-position and one! These include phenolic couplers having an acylamino group at the 7-j-position. Special application 1972-931.0! , same j9-2A
Guco 77 and the same tower 2g? /,? Of the naphthol described in J-! Cyan couplers substituted with a sulfonamide group, an amide group, etc. at the - position also have excellent fastness of colored images, and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing. U.S. Patent No. &,/13.

Yellow-colored magenta couplers described in Japanese Patent Publication No. 7-32 Gua No. 3 or U.S. Pat.
Ori, No. 9.29, No. 3, No. 3.

,2/! No. 1 and British Patent No. 1. Typical examples include the magenta-colored cyan coupler described in No. 3 and No. 2, etc.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in U.S. Pat. , a specific example of a magenta coupler is given in No. j7θ, and European Patent No. 91°570
No. and West German Application Publication No. 3, . 23 & , J-J'
No. 3 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,413/
,! It is described in the λθ issue and the same issue, tit, o and 0°2//. Specific examples of polymerized magenta couplers include:
British Patent No. 2,102,773, US Patent No. 41.
3A7.2 Zako No., Patent Application Sho, 0-7 to θy/, and 0-//3!9.

Specific examples of monomers forming units constituting the polymer of the polymer latex used in the present invention include the following. However, specific examples of the monomer are not limited to these.

[Specific examples of polymer monomers]

(1) Alkyl acrylates (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, etc.) (2) α-substituted alkyl acrylates (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cohetero hexyl methacrylate, ethoxyethyl methacrylate, etc.) (3) Unsubstituted or substituted acrylamide (e.g. acrylamide, methacrylamide, N-butyl methacrylate, N-isopropylacrylamide, N-ethoxyethyl acrylamide, etc.) (4) Vinyl ester (
(e.g., vinyl acetate, vinyl butyrate, etc.) (5) Vinyl halide (e.g., vinyl chloride, etc.)
(6) Styrene or substituted styrene (e.g. styrene,
α-methylstyrene, p-hydroxystyrene, etc.) The above monomers may be contained as the first monomer component, and acrylic acid, methacrylic acid, and itaconic acid may be contained as the second component. Furthermore, other polymerizable vinyl monomers can be contained as a third component. The polymer latex of the present invention has an average particle size of 0
．． 0/～! [mu]m, preferably 0.07 to 7 [mu]m and 1 [mu] to j[mu]m may be mixed. The amount added is j~/jθ weight% based on the emulsion binder (gelatin) added.
It is.

Typical specific examples of the polymer of the present invention will be listed below, but the invention is not limited thereto.

H3 x:y=97:3 − to / − x:y=90:/θ H3 XI y=9! :! x: y=riθ:/θ x:y=9.2: Z-1+2- CH3 x:y:z=e? 0:/θ:10 potassium persulfate,
Ammonium persulfate, tert-butylno ξ-octoate, benzoyl peroxide, isopropyl percarbonate, 2.4t-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydronomyoxide, dicumyl peroxide, azopisisobutyronitrile- '-Azobis(2-amidinopro-ξ)-hydrochloride, etc.

Examples of emulsifiers include anionic, cationic, amphoteric, and nonionic surfactants as well as water-soluble polymers.

Synthesis examples of these compounds are described in Japanese Patent Application No. Sho J/-/90129, pages jj to 60.

Commonly known materials can be used in combination with the photosensitive material element according to the present invention. For example, US Patent No. g, jg θ
l to j number, second number, 399.307, second number 1gθ
No. 7.002, No. 7.173, No. 9. q
3θ, RI No. 23, Japanese Patent Application Sho t/-/F3 GR R 2, 滝昭子/-/RI Ogo No. 29, or cited materials. Color image stabilizers, color mixing inhibitors, ultraviolet absorbers, stain inhibitors, color capri inhibitors, dyes, color development accelerators, crystal plane conversion initiation inhibitors (CR
compound), brightener, surfactant, mordant, binder, etc., in each photosensitive layer, antihalation agent (AH), back layer (BL), intermediate layer (ML), functional photosensitive layer (FL),
It can be used in combination with a single filter layer (YF), a protection layer (PL), a treatment inhibiting substance adsorption layer (ADL), etc.

These layer structures are, for example, Tokkosho &? -/j Geta! No. Tokko Akira! , f-3ri No. 932, Yuaki! 3-32θ72
No., Akira, f3-37θ/za No., Tokukai Akira! Tar/77!
! No. 7, Yushoyoter No. 730731, Yushoyoter/77
! No. 32, Yoshiaki! Day/♂0! ,f,! No., you? 0! ,! No., Yukiaki! Tar/♂2ri No. 17, 滝昭j9−2θyθ3? -g Yo- No., U.S. Patent No. G/♂ri/74, U.S. Patent No. G/, 2ri 4t
Daotsu No., same No. ri/r Otsu O/, same No. gu/♂60//, same No. 2J7.2, same No. gu/73ri No. 7,
Same No. 41/, No. 3-79/7, No. G/Go! 23 Otsu No.
British Patent No. 1J 09B! No., same No./3z9t2,
Same No. 2/3737.2, Patent Application No. 1986-23
No., Japanese Patent Publication No. Shoj9-3737, Japanese Patent Publication No. Sho-G No. 230
No., Showa A/-3t3guj, special application 1986-/! 91O
It is written in t issue etc.

A protective layer is provided, preferably 0°! μ or jμ, particularly preferably the following (1), (2) and (3)
It is to use any of the elements.

(1) Hardening the white layer or other layers by adding a hardening agent represented by the general formula (n).

(2) A dispersion of a water-insoluble, organic solvent-soluble polymer is used to contain an ultraviolet absorber, a color image stabilizer, a mordant, and the like.

(3) Contain vinyl polymer latex particles or inorganic fine powder, preferably average particles (B) containing two or more of different sizes.

The fine inorganic powder is preferably silica gel.

Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer) or the like. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

According to the present invention, the color photographic material has the above-mentioned RD, A
/7 Niri 3 no 2r ~ Kota page and doujin/,! Development processing can be carried out by adapting the usual methods described in the left to right columns of 7/l to the stream-based image forming method of the present invention.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-couamino-N, N-diethylaniline, -N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-guamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-kuami/-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-)luenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-capri agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as In addition, if necessary, preservatives such as hydroxylamine, dialkylhydroxylamine derivatives or sulfites, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol/lz, polyethylene glycol, quaternary ammonium salts, and amines may be added. development accelerators, dye-forming couplers,
Competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids West German patent applications for various chelating agents such as
OLS) 2nd. Ha, 9. Antioxidants such as those described in No. fO may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, /-phenyl-
Known black-and-white developers such as 3- to 9-mono-pyrazolidones such as 3-pyrazolidone or aminophenols such as N-methyl-p-aminephenol can be used alone or in combination for hardening.

After color development, the photographic emulsion layer is usually bleached.

Bleaching treatment may be carried out simultaneously with fixing treatment or may be carried out separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (II), peracids, quinones, nitroso compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (1) or cobal (nl), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-diamino-coprobanol tetraacetic acid; Aminopolycarboxylic acids such as acetic acid, citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates; nitrosophels, etc. can be used. Among these, ethylenedi-7θ-aminetetraacetic acid iron(III) salt, diethylenetriaminepentaacetic acid iron(III) salt and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complexes are particularly useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

In particular, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds having a mercapto group or a disulfide group are preferred.
．． ? Wa 3. F! TR No. 37! No. 73, West German Patent No. 1. Ko90. l? /No. 2, Japanese Patent Publication No. 1983-1999-ta jt3θ
The compounds described in No. 1 are preferred. Additionally, U.S. Pat.
! ! 2.L! Compounds described in No. 3 are also preferred.

These bleach accelerators may be added to the photosensitive material. When bleach-fixing the color photosensitive material for photography according to the present invention,
These bleach accelerators are particularly effective.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfates are commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and mold, various hardening agents, etc. can be added as necessary. Or Photographic Science and Engineering by West (L, E, W
est, Phot, Set.

Eng, ), Vol. 3, 3!9 may be added with the compounds described in -di(/rig, etc.). Addition of a chelating agent or an anti-spill agent is particularly effective.

In the washing process, it is common to use countercurrent washing in tanks of λ class or higher to conserve water. Furthermore, instead of the water washing process,
-t? ! A multi-stage countercurrent stabilization treatment step as described in No. 4t3 may also be carried out. In the case of this step, 2 to 9 countercurrent columns are required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water, Representative examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (benzointhiazolinone, isothiazolone, goutiazoline, etc.) are added as necessary. Various additives such as penzimidase (halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and compounds for the same or different purposes may be used. Two or more types may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and the processing conditions, but is usually 0 seconds to /0 minutes, preferably 20 seconds to j minutes.

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 processing. In order to incorporate it, it is preferable to use various precursors of the color developing agent.

For example, indoaniline compounds described in U.S. Pat. No. 3, Jgj, ji97, U.S. Pat.
No. 92, Research Disclosure/4t? ! θ issue and same/! /, the thick base type compound described in No. 3-9,
Aldol compounds described in US Patent No. 39241, metal salt complexes described in US Pat.
In addition to the urethane compounds described in No. 3-736g and 2L5', various salt-type precursors can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-
3-pyrazolidones may be incorporated.

The various processing solutions used in the present invention are typically used at a temperature of 33°C to 30°C, which is used at /θ'C-5o°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, it is possible to improve image quality and stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent Nos. 2 and 22, No. 77θ or U.S. Patent No. 3. Otsu 7E, Q9? Treatment using cobalt intensification or hydrogen peroxide intensification as described in the above may be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

In the photographic processing of the black photographic material of the present invention, known processing liquids can be used. Processing temperature is normal/r0
The temperature is selected between C and so 0c, but the temperature may be lower than /♂0C or higher than jθ0C. Forming a silver image depending on the purpose. For details, see Research Disclosure Vol. 77, A/7, page 3, page 57 of Volume 1, A7.5'7/l, left. The method described in the right column can be applied to the stream-based image forming method of the present invention for development processing.

The photosensitive material of the present invention exhibits particularly remarkable effects when a black and white developer preferably having a low pH is used.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), and aminephenols (e.g. N-methyl-p-aminephenol). They can be used alone or in combination. Further, the effect is remarkable when the pH is between 7.s and 9.2.

Next, preferred embodiments of the present invention will be shown.

(1) A photosensitive material provided with a process-inhibiting substance adsorption layer (ADL) on any of the protective layer, intermediate layer, no-ration prevention layer, or back layer is developed with a processing liquid stream to form an image. .

ADL has JP-A-Jθ-, 23, 22r, open! θ−
Otsu! No. 230, gap, </-! No. 1,3416, % intercondylar 60-/! 9/θ Otsu and U.S. Patent No. 37, l! '/3
Use the materials listed in the issue.

(2) An image is formed by developing using a developing processor according to the present invention, which is equipped with a member having a function of capturing the processing inhibiting substance using the above-mentioned processing inhibiting substance.

(3) A photosensitive material containing fine particles of a polymer coupler or polymer latex in a photosensitive layer, a protective layer, an intermediate layer, or a back layer is developed with a stream of a processing solution to form an image.

Next, examples of the present invention will be shown. In particular, a color image forming method will be described, but the black and white image forming method will be easily understood from this example. Examples 1-2 show the method of preparing silver halide multi-structure grains, the method of carrying out color development processing using a stream, and the effects of each or a combination thereof on a GL coated photosensitive material. Example 2 shows how to make a color photosensitive material and the implementation method and effects of the color image forming method according to the present invention. However, the present invention is not limited to this.

Example-/ (Preparation of silver halide emulsion) An aqueous solution containing 30 g of inert gelatin, 6 g of potassium bromide, and 7 liters of distilled water was stirred at θ0C, and silver nitrate s, og was added thereto. 35 cc of a dissolved aqueous solution and 3 ICQ of an aqueous solution containing 3.2 g of potassium bromide and 0.9 J" g of potassium iodide were each mixed at a flow rate of 70 cc/min.
After adding for a second, pAg was raised to /θ and ripened for 30 minutes to prepare a seed emulsion.

Next, silver nitrate/41. A predetermined amount of an aqueous solution/l in which fg is dissolved and an equimolar amount of an aqueous solution of a mixture of potassium bromide and potassium iodide are added at a predetermined temperature, a predetermined pAg, and an addition rate close to the critical growth rate to form a tabular core emulsion. was prepared. Subsequently, equimolar amounts of the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in preparing the core emulsion were added at a rate close to the critical growth rate to form the core. Coated core/shell type silver iodobromide flat plates A, E and G were prepared. Also the first European patent Gua and Otsu! Referring to the method described in No. A, a core/shell (double structure) cubic emulsion F in which the iodine content of the core portion was higher than the iodine content of the shell portion was prepared. The temperature, addition speed, and pAg during addition were adjusted to obtain the desired average size and aspect ratio of each emulsion.

The pAg was adjusted so that the aspect ratios of emulsions A, B, C, D, G, and H were around 2, and the total iodine content (excluding G) was set to 3 moles. The particle size was adjusted so that the equivalent sphere diameter for both A and H was θ, /μ. The grain size distributions of Emulsions A to D and GH are considered to be almost the same, with a relative standard deviation of nearly 30%.

Emulsion G was prepared as an example in which the iodine content of the core was relatively too low, and Emulsion H was prepared as an example in which the iodine content of the shell was relatively too large.

Characteristic values of emulsions A and H (average iodine content, core iodine content, shell iodine content, aspect ratio, grain size,
The core/shell ratio is shown in Table 1.

The calculated value is shown after confirming that the measured value of the average iodine content obtained from X-ray diffraction of silver halide annealed at 20θ0C for 3 hours and the calculated value almost agree with each other. The iodine contents of the core and shell parts are calculated values. The particle size (equivalent sphere diameter) was determined using a Coulter Counter (Coulter Co., Ltd.), and the aspect ratio was determined according to the method described in Japanese Patent Application Laid-Open Publication No. 2002-39292. The core/shell ratio is a calculated value. The interparticle iodine distribution is described in European Patent No. 74t7. ? J
It was determined according to the method described in No./A. Double structure was determined by the method described in JP-A-60-7413337.

Each of these emulsions was optimally chemically sensitized using sodium thiosulfate and chloroauric acid, respectively, and spectrally sensitized using an optimal amount of a methanol solution of sensitizing dye (1).

(Preparation of Sample) An emulsion layer and a protective layer were provided on a triacetyl cellulose film support provided with an undercoat layer according to Table 2.

Samples/liter were obtained.

−? /- -J', 2- Table 2 (1) Emulsion layer/emulsion... Emulsions A to H shown in Table 7 (silver,
/×/θ−2 mol/m2) 0 coupler = (/, s×10−3 mol/m2) o tricresyl phosphate (/, 10 g/m2) “Zera f7 (2,30 g/m2) ( 2)
Protective layer 'J+4t-dichlorotriazine-O-hydroxy-8
-Triazine sodium salt (0, #g/m2) 0 gelatin (/, J'Og/m2) (color development process) These samples/~10 were left for 77 hours under the conditions of qo 0c and relative humidity 7θ% After that, exposure for sensitometry was applied, and the next color development process was performed.

The concentration of the treated sample was measured using a green filter.

Process Processing time Processing temperature Replenishment amount Color development
2 minutes 0°C 300ml/m2 bleach fixing 2 minutes 00C3θθml/m2 water washing 7 minutes 3
0°C 211/m2 Total process j minutes The composition of the treatment liquid used is as follows.

(Color developer) (P/) (Replenisher) Diethylenetriaminepentaacetic acid /, 0 /, θ/-hydroxyethylidene-/, /- diphosphonic acid 3.0 3. θ/, 3-diaminoprobanol ri, 0 ri, θ glutamate sodium 3. Oj, θ potassium carbonate
30.0 30. θ potassium bromide
/,G -Hydroxylamine sulfate K,G 3.0G (N-
Ethyl-β-hydroxyethylamino)-comethylaniline sulfate ri,j! , θ Add water /, 01 /, 01 pH Add sodium hydroxide 10.0. f 10.4t,! (
Bleach-fix solution) (pco) Ethylenediaminetetraacetic acid ferric ammonium dihydrate jθ, θethylenediaminetetraacetic acid dis=! j− Thorium salt! , θ Sodium sulfite /, 2.0 Ammonium thiosulfate aqueous solution (7 θ) 2 O θ, Oml acetic acid (9
%) s, o ml water added /, 0/3 pHj, θ First, a modified product of Fuji Film's color paper processing machine (F
PRP-sθ2L).

A schematic diagram of the processing machine at this time is shown in FIG. (Conventional Method A) Next, the processing tank shown in Figure 1 was used as a color developing solution. Figure 2 shows the stainless steel tank body and roller (
Figure 2-7), PVC hollow rack, roller, and handle (
Figure U-2) shows a thin slit-shaped developing tank. The developer solution between the slits is maintained at θ0C by the hot water. When processing a photosensitive material, the photosensitive material is bonded in advance to a leader with a through hole, and the photosensitive material is passed between the syslits using a separately provided driving force for processing.

The thickness of the slit at this time is about g mm, which is the standard for photosensitive materials.
The width of the refill port (H/) was 7 m, and the length of the refill port (D) was approximately 336 am.

The developer in the tank was about 3.21 ml. Conveying speed is /
, rm1 minute.

Bleach-fix solution and water washing are processed using conventional processing tanks. (For example, after P2 in FIG. 1) The transport speed of the sensitive material in the color developing solution at this time is /.

sm1 minute. The color developer is replenished from the replenishment port (H/), and the amount of light supplemented per minute is 4tsm.
It took 1 minute. Therefore, it is estimated to be 7.5 cm/minute from the cross-sectional area of the developing slit portion.

The difference in transport speed between the photosensitive material and the processing solution is approximately 160 cm.

ICm=2θ:/. (Treatment method B according to the present invention
) A color developing solution was applied under the conditions of (A) and (B), the initial photographic performance was examined, the film was left for another week, and the photographic performance was examined again after development.

Table 2 shows data such as photographic properties after a week of aging.

(Result) Like sample A7 (emulsion G), the iodine content of the core is 3.
When it becomes malty, the graininess worsens. Also, sample A, 11'
When the iodine content of the shell is too high (zmolti) as in (emulsion H), development progresses slowly, resulting in low sensitivity and low gamma. In general, processing method B according to the present invention has higher sensitivity than processing method A, and has a relatively superior graininess. In particular, when emulsions A to F according to the present invention are used, the effect can be sufficiently exhibited in practice. Furthermore, tabular grains have high transparency when compared with the same amount of silver halogenide, so that the sharpness of images can be improved. For example, the spectral transmittance of θθnm when using Cuci light is about 0% for sample AF, while samples A to D with an aspect ratio of 7 are about 70 to 7! Met.

In the developing method B of the present invention, after a week of aging, compared to the conventional developing method A, about /,! It makes you feel twice as tall. This effect is more remarkable when the emulsion of the present invention is used than when the emulsion of the comparative example is used.

A similar trend was observed for gamma.

The graininess is slightly worse in the developing method (B) of the present invention than in the conventional developing method (A). This is considered to be due to the high sensitivity and high gamma in the developing method of the present invention. However, when using the developing method of the present invention and the combination of the emulsions of the present invention, the graininess was not significantly deteriorated despite the high sensitivity and high gamma.

The analysis results of the developer are shown in Table y.

The analysis results also show that after y weeks of aging, the method of the present invention shows little deterioration when turning deep red, and is a simple and hassle-free treatment system.

Example 2 (Preparation of silver halide emulsion) A core/shell type silver halide emulsion according to the present invention was prepared by patent application Sho/-, 2/lr! The halogen composition and pAg were adjusted according to the examples in the above issue, and the chemical ripening conditions were adapted to obtain various silver halide emulsions shown in Table 5.

(Preparation of sample) A highly sensitive multilayer color negative photographic material was prepared by coating the following layers 1 to 1 on a cellulose triacetate film support. The total silver content is
The total area was 027m2. This photosensitive material is designated as sample 10/. Total film thickness is approximately 2g.

It was jμ.

1st layer: antihalation layer black colloidal silver 0. /za27m2 Ultraviolet absorber C-/θ, /, 2g/m2 Same C
−λ θ , /2g/m20il−/
Gelatin layer containing θ, 010il-, 20,07 gelatin /, 027m2 Thickness approximately /, qμth λ layer: Intermediate layer 2,! -G-t-pentadecylhydroquinone θ, /rg/m2 coupler
C-30,7727m2 0il-/θ,/-9 goo silver iodobromide emulsion (1 molt silver iodide, average grain size 0°02μ) 0. /rg/m2 Gelatin θ, rg/m2 Gelatin layer Film thickness: approx. 0.9μ 3rd layer: First red-sensitive emulsion layer Silver iodobromide emulsion Ru-/ 0.2Ωg/m2 Sensitizing dye ■... 7.0x/θ-5 moles of sensitizing dye per 1 mole of silver 7.0x/θ-5 moles of sensitizing dye ■... per 7 moles of silver, θx/θ-5 moles of sensitizing dye ■... per mole of silver Ko, t! "×70-5 mol sensitizing dye■...Co, θ×10-5 mol coupler per mol of silver C-ri θ, 093 g/m2 coupler C-s θ, 3/g/m2 coupler C-
t θ, 010g/m2 Polymer P-/
・0.030il-,?
θ, 0/2-9 Yo- Gelatin /・Gelatin layer containing Og/m2 Film thickness Approximately/, μth layer: Red-sensitive emulsion layer Silver iodobromide emulsion Rm-/ /, 2g/m2 increase Sensitizing dye I... per 7 mol of silver] ~, f, 2 x 10-5 mol sensitizing dye ■... per 1 mol of silver /, it x 10-5 mol sensitizing dye ■...・2,/×10-5 mol per 1 mol of silver Sensitizing dye■.../, J-X/θ-5 mol coupler C-ri 0.10 g/m2 coupler C-s θ, 0/g/m2 coupler C-
7o, θrigo 27m2 0il-/ θ, /, fOi
1-3 θ, gelatin layer containing 0.2 gelatin/, IlfTg/m2 Film thickness: approx. Layer: Third red-sensitive emulsion layer silver iodobromide emulsion RO-/, 2. θg/m2 sensitizing dye per mole of sensitizing dye silver! ,! ×70-5 mol sensitizing dye ■.../, ×/θ-5 mol per 1 mol of silver Sensitizing dye ■...Co, ko ×/θ-5 mol increase per 1 mol of silver Sensitive dye ■...X10-5 mole coupler per 1 mole of silver C-s□, θ41rytg/m2 coupler
C-70,/Ig/m2 Polymer P-/o, oloil
-, 2o, or gelatin layer containing 3.0 g/m2 Thickness approx. 3. rμ G layer: Intermediate gelatin layer Film thickness approx. 0.2μ 7th layer:
First green-sensitive emulsion layer Silver iodobromide emulsion Gu-/o, ssg/m2 Sensitizing dye V...3, rX/θ-4 mol per 1 mol of silver Sensitizing dye ■... 1 silver 3.0 x 10-5 mol per mol Sensitizing dye ■.../2 x 10-4 mol per mol of silver Coupler C-do 0. ．． 29g7m2 coupler C-9o, θ 027m2 coupler C-/θ θ, 0 evening rg/m2 coupler C-// θ, 0 evening and 27m20il-/
0. ,! gelatin
0. ,? Gelatin layer containing g/m2
Film thickness: approx. 71.2μ 1st layer: Green-sensitive emulsion layer silver iodobromide emulsion Gm-//, θg/m2 sensitizing dye, 7×/θ-4 mol per 1 mol of sensitizing dye silver Sensitizing dye ■...λ, /×/θ-5 moles per 7 moles of silver Sensitizing dye ■...r, j×/θ-5 moles per mole of silver Coupler C-ero , ,2sg/m
2 coupler C-ta θ, θ/ 3 g/m
2 coupler C-/θ θ, θθri g/m2 coupler C-// o, o//g/m20i1-10
．． 2 Gelatin /・! Gelatin layer containing g Film thickness: approx. 2.0 μ Second layer: Third green-sensitive emulsion layer Silver iodobromide emulsion Go-/, 2.0 g/m 2 Sensitizing dye ■...3 per mole of silver .0 x 70-4 mol sensitizing dye■...Recognized for 1 mol of silver, x/θ-5 mol Sensitizing dye■...W, j x/θ-5 for 7 mol of silver Molar coupler C-/, 2o, θ70g/rn2 coupler
C-wa θ, 0/3g/m20iI-/
θ, recognized θ0il-20,0! Gelatin 3・Gelatin layer containing Og Thickness approx. 3. μ 70th layer ゛Yellow filter, yellow colloidal silver θ, θKg/m2, j-
D-t-pentadecylhydroquinone o, 03/g/m20il-/
Gelatin layer containing θ, 3 Thickness: Approximately θ, 9μ 1st/layer: First blue-sensitive emulsion layer Silver iodobromide emulsion Bu-/ 0.32g7m2 coupler C-73θ, Otsu cf'g/m2 coupler C-/ 4
t θ, 030 g/m 20il-/
θ, 2 gelatin
Gelatin layer containing 0.sg
Film thickness: approx. 7.3μ 1st-2nd layer; 3rd blue-sensitive emulsion layer Silver iodobromide emulsion B m -/ 0.21g7m2 Coupler C-/3 0.22g7m20il-/
θ, θ7 sensitized color sensitizing dye silver 1
Gelatin layer containing 2.2×/θ−4 mol gelatin 0.3 sg/rn2 Thickness: approx. θ, 7 μ 73rd layer: Gelatin layer Film thickness: approx. θ 0.2 μ 1st layer: 3rd blue color Emulsion layer Silver iodobromide emulsion Bo-/ θ, fOg/m2 coupler C-7j O,/9g/m2 coupler C
-7s 0.007g7m20il-/
o, os polymethyl methacrylate particles (average particle size θ, cojμ) θ, Osg/m2 Sensitizing dye■
... Gelatin layer containing 2.3x/θ-4 mol gelatin/, 2g/m2 for the sensitizing dye layer Film thickness: Approximately 70gμ 1st layer, 7th protective layer Ultraviolet absorber C-/0. /'Ig/m2 UV absorber C-, zo,, 2 layers g/m20il
−/θ, 010il −,
2θ, θ/gelatin θ, t Gelatin layer containing 9g/m2 Film thickness: approx. 7.0μ 1st g layer: 2nd protective layer polymethyl methacrylate particles (diameter 2.5μ) θ, θJig/m 2 Silver iodobromide emulsion ( Silver iodide comolti, average grain size 00 07μ) 0.3θg/m2 Formalin scavenger 8-/θ, sg/m2S-,2
Gelatin layer containing gelatin 0.30g/m2 Film thickness: approx./, 0μ Each layer was coated with a gelatin hardener C-/Goya surfactant in addition to the above composition.

-10+2= Compound C-/Polymer C-,2 2=N (ku)
IC,l
Q\
He ox I n Q Q To Country Q C-/, 2 C-/3 C-7<t C-/j C-/Go CH2=CH-802-CH2-CH2-CH2,5o
2-CH=CH2S-/CH3 Fuki I S-Co ■ Oil-/ Tricresyl phosphate 0i1-2 7 Diptyl talate 0i1-3 7 Bis(,2-ethylhexyl) talate sensitizing dye ■ -10 and - ■ 2H5 -/θ tar (color development process) These photographic elements use a tungsten light source, and the color temperature is adjusted to 41/θθ0K using a filter.
After giving a 10θ second exposure, 3
Development processing was performed at 0C.

Color development - minutes 70 seconds Bleach White 3 minutes/! seconds Bleach White 3 minutes/! seconds Fixed arrival time: 20 seconds Water Washing 3 minutes/j seconds Safe, stable, 7 minutes, 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer (N/) (replenisher) diethylenetriaminepentaacetic acid /, og (/, θg)/-
Hydroxyl cylidene-/.

/-Diphosphonic acid, Og <2.0g) Sodium sulfite, θg 0.0g) Potassium carbonate, 3θ,θg (3,2,θg) Potassium bromide /, og (0.9g) Hydroxylamine sulfate , ri g (3-tg) Gu(N-ethyl-N-β-hydroxyethylamino)-kotathylaniline sulfate ri, sg D, 2 g) Add water /, θg </, 011) pH 1
0, θ (pH/θ, 3j) Bleach solution (N2> (Replenisher) Ethylenediaminetetraacetic acid ferric ammonium salt 700.0 g (100, Og)
Ethylenediaminetetraacetic acid disodium trilam salt 10. Og (10, og) ammonium bromide /ta θ, Og (/sO, Og) ammonium nitrate 10. θg (/θ, θg) Add water to /, 01j (/, θ1) pH, 0
(pHj, 4) Fixer (Nj) (Replenisher) Ethylenediaminetetraacetic acid disodium trilam salt y, og (/, og) Sodium sulfite ri, og (4t-og) Ammonium thiosulfate aqueous solution (7o%) i7r, oml ( /7r
, oml) Sodium bisulfite 1//3-ml, 6g
(ri, nig) add water /, ol
(/-0l) pHd, & (pH O, ni) Stabilizer (N4t) (Replenisher) Holimarin (g0%) , :z, oml (a, oml)
Polyoxyethylene-p-monononylphenyl ethyl (average type /θ) 0.3g (0.3g) Add water and i,ol (/, oll) Processing method is shown in Figure 3. Manufactured by Fuji Film. A modified color negative processor (F N CP-tθ0) was used. (
On the other hand, for the color developing part (N/), use the developer tank shown in Figure 2 and refill the color developer replenisher from the replenishment port (H/) 9/10, and then from the refill port (H, 2). Add 3 mg/l of methylbenzotriazole to the color developer replenisher ///
For the other baths, the modified processor shown in FIG. 3 was used.

(Processing method B according to the present invention) As a type sensitive material, Fuji Film's Sue/ξ-HR<20
0 film and sample /θ/ as test sensitive material at relative humidity 4
After being allowed to stand for 2 hours under conditions of tj%, sensitometric exposure was performed and processing was performed using a combination of processing methods (A) and (B).

The results obtained are shown in Table 2.

Compared to the conventional processing method (A), the processing method (B) of the present invention has higher sensitivity and lower minimum density (base density fog) for the sample /θ/ of the present invention than the conventional processing method (A). It's also expensive.

That is, by combining the photosensitive material of the present invention and the processing method of the present invention, an unexpected synergistic effect was obtained.

It was also found that treatment method (B) generally had a lower minimum concentration and better graininess (higher MTF) than treatment method (A).

The color development process of the present invention can be carried out by installing and modifying the processing tank, rack, and roller for the present invention shown in FIG.

[Brief explanation of drawings]

FIG. 1 schematically shows a sectional view of a color processing machine and a processing system as a comparative example of the color processing system of the present invention. A processing tank and a rack provided for carrying out the processing according to the present invention are installed in the processing section pHte of the color developing processing machine. FIG. 2 is a sectional view of the processing tank and rack. The second figure is a cross-sectional view of the processing tank and roller of the present invention, and the first figure is a cross-sectional view of the rack, roller, and handle of the present invention. (See Example 7) FIG. 3 schematically shows a sectional view of a color developing processor shown as a comparative example and its processing system. (Example-
Figure 1 shows the relationship between the tank capacity and tank opening degree (K) of a color developing processor. In Figure 1, P/: color development (tank liquid volume &01), P2 = bleach-fixing (tt 3θl), W: water washing (z, 20 l x 3), respectively. In Fig. 2, T Handle H/ Replenishment port H, 2〃 R/ Roller (fixed to the tank body) R, 2# () R31 (attached to the rack) D Overflow port are shown, respectively. In FIG. 3, N/color development stop, N2 bleaching, W/intermediate water washing, N3 fixing, and two washings, N, stability, are shown, respectively. Patent Applicant: Fuji Photo Film Co., Ltd. -//Taichi, Figure 2, Figure 4, Tanktsu Shifu 9 (1) Procedural Amendment Document, April 1985/Left Date [Yes] 1. Indication of the Case 1988 Special Edition Application No. 70006 2. Title of the invention: Image forming method 3. Relationship with the person making the amendment Patent applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Bekaede ν 4. Subject of the amendment: Detailed description of one invention in the specification The description in Column 5 of ``Detailed Description of the Invention'' in the Statement of Contents of Amendment is amended as follows. 1) After page 13, line 20, ``A core with a multilayer structure is, for example, a core obtained by providing a layer with an average silver iodide content/tamol% on silver bromide, or an average silver iodide gold *20 These include a core obtained by providing 3 mol % of N on maltisilver iodobromide, and a core obtained by providing a layer with a different structure obtained by conversion.'' 2) Correct "Sho 7 ≠" on the Vth page/Vth line to "Sho 7 Geta". 3) On page 5'1, the text from "Applicant" on line ≠ to "Specification" on line /j is amended to read [Japanese Patent Application No. 61-142113]. - Ko - 1985 ≠ month tLf 1

Claims (1)

[Claims] (1) In an image forming method using a photosensitive material comprising a silver halide photosensitive layer provided on a support, [1] The core of the silver halide grains contains 4 mol% to 40 mol% silver iodide. [ 2] Image formation characterized in that in at least one step of the development processing step, the photosensitive surface of the photosensitive material is in contact with a stream of processing solution without being exposed to substantially free air. Method.